CN102653396A - 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
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- CN102653396A CN102653396A CN2011100498047A CN201110049804A CN102653396A CN 102653396 A CN102653396 A CN 102653396A CN 2011100498047 A CN2011100498047 A CN 2011100498047A CN 201110049804 A CN201110049804 A CN 201110049804A CN 102653396 A CN102653396 A CN 102653396A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002096 quantum dot Substances 0.000 title claims abstract description 18
- 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 51
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- 229910052737 gold Inorganic materials 0.000 claims description 13
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 11
- 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
- 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
- 238000003756 stirring Methods 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
- 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
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- 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
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- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract 1
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- TYAMCPIKMIGMQC-UHFFFAOYSA-N 2-perylen-1-ylethanethiol Chemical group SCCC1=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45 TYAMCPIKMIGMQC-UHFFFAOYSA-N 0.000 description 4
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
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- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
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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 pass through chemical process (as from the graphene oxide reduction) at present by batch and low consumption production.In this method, graphene oxide can through to graphite crystal oxidation peel off and obtain, through after reductive agent, heat, the electrochemical reaction reduction, can obtain Graphene (being the reductive graphene oxide) again.Unique two-dimension plane structure and outstanding electricity, optics, mechanics and the chemical property of Graphene makes it become one type of atomic scale template that has the structure novel graphite thiazolinyl nano composite material of potentiality.Such as, after graphene film was modified by metal nanoparticle, its inherent various types of properties can be by appropriate regulation to adapt to its application in fields such as catalysis, energy generation and storage, photoelectronics, transmitters.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.
Though the graphene film mixture that metal nanoparticle is modified has been obtained certain progress so far, to modified metal size of particles, homogeneity, density, still there is great challenge in the aspects such as dispersiveness and performance of modifying back mixture.A large amount of oxy radicals on graphene oxide surface make graphene oxide that good solvability arranged in the aqueous solution, and the reaction site of surface chemical modification can be provided.Yet for the Graphene with high-transmission performance, graphene oxide is an isolator.And the oxy radical of random distribution can cause the random distribution of the metallics in the chemically modified.Can reply conductivity significantly after the graphene oxide chemical reduction, but but the gathering that can produce graphene film because of pi-pi accumulation and hydrophobic interaction makes the dispersiveness decline in solution.Continue again the graphene film of monolithic is modified with regard to being difficult to like this.Therefore, the graphene film that the metal nanoparticle of most of report is modified all is in state of aggregation, can't be adapted to the requirement of types of applications.
Self-assembly is a kind of method of effective structure metal-graphite alkene mixture.In this method, a kind of suitable link molecule (such as organic molecule, DNA, protein) is used to link metal nanoparticle and graphene film.The metal nanoparticle that this method normally will prepare in advance is linked on the graphene film, but can't effectively control its size, systematicness, density yet generate metal nanoparticle for original position on graphene film.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, the graphene film matrix material and the in-situ preparation method that provide a kind of metallic nanodots rule to modify with polymolecularity.
Graphene film matrix material with metallic nanodots rule modification of polymolecularity is made up of graphene film and the metallic nanodots that is modified at the graphene film surface; Be connected through containing sulfydryl De perylene diimide derivative molecular between metallic nanodots and the graphene film; Wherein: the particle diameter of metallic nanodots is 1～3 nm, and the plane of graphene film is hundreds of square nanometers to a number square micron.
The described sulfydryl De perylene diimide derivative molecular molecular structural formula that contains is:
N is the length of alkyl chain between inferior acid amides and the sulfydryl, n=2 or 12.
The described preparing method's who contains sulfydryl De perylene diimide derivative molecular step is following:
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
2Protection is down 100～150 ℃ of stirring reactions 3～12 hours;
2) reaction soln is joined in the absolute ethyl alcohol of 500～1000 mL precipitate, filter and collect filter residue, it is 5～10% sodium hydroxide solution washing 3～5 times that filter residue uses weight percent concentration again, filter, until filtrating for colourless;
3) filter residue becomes neutral with the pH value of deionized water wash to filtrating, and is dry in 70 ℃ of vacuum drying ovens, obtains containing the perylene diimide derivative molecular of sulfydryl.
Said metallic nanodots is gold nano point, silver-colored nano dot, platinum nano dot or palladium nano dot.
The step of in-situ preparation method with graphene film matrix material that the metallic nanodots rule of polymolecularity modifies is following:
1) 2.5～5 mg contain sulfydryl De perylene diimide derivative molecular after the dissolving of 1～2 mL deionized water for ultrasonic; 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 not tolerant back in 30～60 ℃ of stirred overnight, obtains being contained the graphene oxide sheet aqueous solution that the perylene diimide derivative molecular of sulfydryl is modified;
2) contain to 10～20 mL that to add 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 in the graphene oxide sheet aqueous solution that sulfydryl De perylene diimide derivative molecular modifies be 28% ammonia soln; Rock mixing solutions after 3～5 minutes in 90～100 ℃ of stirring reactions 1～3 hour; The dark solution that obtains is to contain the graphene film aqueous solution that sulfydryl De perylene diimide derivative molecular is modified, in the product excessive Hydrazine Hydrate 80 with contain sulfydryl De perylene diimide derivative molecular and remove through the dialysis of 3500～5000 molecular weight dialysis tubings;
3) 1～5 mL, 0.1 mg/mL Thiovanic acid joins in the graphene film aqueous solution of 5～25 mL thiol molecule modification; Under agitation add 0.16～0.8 mL, 10 mM aqueous metal salts continuation reaction and spend the night, obtain having the regular graphene film nano composite material aqueous solution of modifying of metallic nanodots of polymolecularity.
1) metallic nanodots can not destroy the chemical structure of Graphene through containing the non-covalent graphene film surface that is linked at of sulfydryl De perylene diimide derivative molecular, can not reduce its electricity transport property.
2) metallic nanodots evenly distribution of rule on graphene film, nano dot is of a size of 2 nm 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 that obtains is modified has dispersiveness good in the aqueous solution, aggregate and precipitate can not take place, and makes the further application of this mixture become possibility.
Description of drawings
Fig. 1 is the low range transmission electron microscope photo with regular graphene film nano composite material of modifying of metallic nanodots of polymolecularity.
Fig. 2 is the high magnification transmission electron microscope photo with 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 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 regular graphene film nano composite material of modifying of metallic nanodots of polymolecularity.
Fig. 6 is the Au4f X-ray photoelectric subgraph spectrum with 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 De perylene diimide derivative molecular and self-assemble to graphene oxide sheet surface introducing sulfydryl; Obtained the graphene film of sulfydryl modification by the reduction of the graphene oxide sheet of sulfydryl modification; Add the nominal price metal-salt and generate metallic nanodots, obtain the graphene film nano composite material of modifying by metallic nanodots in the reduction of the sulfydryl site on graphene film surface.
Following embodiment further specifies of the present invention, rather than limits scope of the present invention.
Embodiment 1:
(1) contain sulfydryl De perylene diimide derivative molecular N, N '-two (preparing method's of 2-mercaptoethyl) perylene diimide step is following:
(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 the 10 mL quinoline, in N
2Protection is down 100 ℃ of stirring reactions 3 hours;
(b) reaction soln is joined in the absolute ethyl alcohol of 500 mL precipitate, filter and collect filter residue, it is 5% sodium hydroxide solution washing 3 times that filter residue uses weight percent concentration again, filter, until filtrating for colourless;
(c) filter residue becomes neutral with the pH value of deionized water wash to filtrating, and is dry in 70 ℃ of vacuum drying ovens, obtains N, N '-two (2-mercaptoethyl) perylene diimide molecule.
(2) N, N '-two (preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film:
(a) 2.5 mg N; (2-mercaptoethyl) perylene diimide is after the dissolving of 1 mL deionized water for ultrasonic for N '-two; Join 10 mL, 0.5 mg/mL graphene oxide aqueous solution, ultrasonic 1 hour of mixing solutions, 3000 rpm are centrifugal to go out not tolerant back in 30 ℃ of stirred overnight; Obtain by N N '-two (the graphene oxide sheet aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification;
(b) to 10 mL N; N '-two (adds 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 and is 28% ammonia soln 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 that obtains is to contain the graphene film aqueous solution that sulfydryl De perylene diimide derivative molecular is modified, in the product excessive Hydrazine Hydrate 80 with contain sulfydryl De perylene diimide derivative molecular and remove through the dialysis of 3500 molecular weight dialysis tubings;
(3) preparation of grapheme modified of gold nano point:
1 mL, 0.1 mg/mL Thiovanic acid joins 5 mL N; N '-two is (in the graphene film aqueous solution that 2-mercaptoethyl) perylene diimide is modified; Under agitation add 0.16 mL, 10 mM aqueous solution of chloraurate continuation 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 De perylene diimide derivative molecular N, N '-two (preparing method's of 2-mercaptoethyl) perylene diimide step is following:
A) 1 weight part 3,4,9,10-perylene tetracarboxylic dianhydride, 1 weight part 2-mercaptoethylamine and 1 weight part Glacial acetic acid zinc join in the 20 mL quinoline, in N
2Protection is down 150 ℃ of stirring reactions 12 hours;
B) reaction soln is joined in the absolute ethyl alcohol of 1000 mL precipitate, filter and collect filter residue, it is 10% sodium hydroxide solution washing 5 times that filter residue uses weight percent concentration again, filter, until filtrating for colourless;
C) filter residue becomes neutral with the pH value of deionized water wash to filtrating, and is dry in 70 ℃ of vacuum drying ovens, obtains N, N '-two (2-mercaptoethyl) perylene diimide molecule.
(2) N, N '-two (preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film:
A) 5 mgN; (2-mercaptoethyl) perylene diimide is after the dissolving of 2 mL deionized water for ultrasonic for N '-two; Join 20 mL, 0.5 mg/mL graphene oxide aqueous solution, ultrasonic 3 hours of mixing solutions, 5000 rpm are centrifugal to go out not tolerant back in 60 ℃ of stirred overnight; Obtain by N N '-two (the graphene oxide sheet aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification;
B) to 20 mL N; (hydrazine hydrate solution and the 150 μ L concentration expressed in percentage by weights that add 14 μ L concentration expressed in percentage by weights in the graphene oxide sheet aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification and be 35 % are 28% ammonia soln to N '-two; Rock mixing solutions after 5 minutes in 100 ℃ of stirring reactions 3 hours; The dark solution that obtains is N; N '-two (the graphene film aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification, in the product excessive Hydrazine Hydrate 80 with contain sulfydryl De perylene diimide derivative molecular and remove through the dialysis of 5000 molecular weight dialysis tubings;
(3) preparation of grapheme modified of gold nano point:
5 mL, 0.1 mg/mL Thiovanic acid joins 25 mL N; N '-two is (in the graphene film aqueous solution of 2-mercaptoethyl) perylene diimide molecular modification; Under agitation add 0.8 mL, 10 mM aqueous solution of chloraurate continuation 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) contain the N of sulfydryl, N '-two (preparing method's of 2-sulfydryl dodecyl) perylene diimide step is following:
Except that raw material replaces the Thiovanic acid with the sulfydryl amino dodecane, other experimental procedure is with embodiment 1.
(2) N; N '-two (the preparation of 2-sulfydryl dodecyl) perylene diimide molecular modification graphene film: remove reaction raw materials and use N; (2-sulfydryl dodecyl) perylene diimide replaces N to N '-two, and (outside the 2-mercaptoethyl) perylene diimide, experimental procedure is with embodiment 1 for N '-two.
(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) contain the N of sulfydryl, (preparing method's of 2-sulfydryl dodecyl) perylene diimide step: except that raw material replaces the Thiovanic acid with the sulfydryl amino dodecane, other experimental procedure is with embodiment 2 for N '-two.
(2) N; N '-two (the preparation of 2-sulfydryl dodecyl) perylene diimide molecular modification graphene film: remove reaction raw materials and use N; (2-sulfydryl dodecyl) perylene diimide replaces N to N '-two, and (outside the 2-mercaptoethyl) perylene diimide, experimental procedure is with embodiment 2 for N '-two.
(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 De perylene diimide verivate N, (preparation of 2-mercaptoethyl) perylene diimide: experimental procedure is with embodiment 1 for N '-two.
(2) N, (preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film: experimental procedure is with embodiment 1 for N '-two.
(3) preparation of grapheme modified of silver-colored nano dot:
Except that the reaction raw materials metal-salt was Silver Nitrate, other experimental procedures were with embodiment 1, and transmission electron microscope confirms to obtain having the regular graphene film nano composite material aqueous solution of modifying of silver-colored nano dot of polymolecularity.
Embodiment 6:
(1) contain sulfydryl De perylene diimide verivate N, (preparation of 2-mercaptoethyl) perylene diimide: experimental procedure is with embodiment 1 for N '-two.
(2) N, (preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film: experimental procedure is with embodiment 1 for N '-two.
(3) preparation of grapheme modified of platinum nano dot:
Except that the reaction raw materials metal-salt was platinum nitrate, other experimental procedures were 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 De perylene diimide verivate N, (preparation of 2-mercaptoethyl) perylene diimide: experimental procedure is with embodiment 1 for N '-two.
(2) N, (preparation of 2-mercaptoethyl) perylene diimide molecular modification graphene film: experimental procedure is with embodiment 1 for N '-two.
(3) preparation of grapheme modified of palladium nano dot:
Except that the reaction raw materials metal-salt was Palladous nitrate, other experimental procedures were 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 (5)
1. graphene film matrix material that the metallic nanodots rule with polymolecularity is modified; It is characterized in that forming by graphene film and the metallic nanodots that is modified at the graphene film surface; Be connected through containing sulfydryl De perylene diimide derivative molecular between metallic nanodots and the graphene film; Wherein: the particle diameter of metallic nanodots is 1～3 nm, and the plane of graphene film is hundreds of square nanometers to a number square micron.
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 sulfydryl De perylene diimide derivative molecular molecular structural formula that contains is:
N is the length of alkyl chain between inferior acid amides and the sulfydryl, n=2 or 12.
3. the graphene film matrix material that a kind of metallic nanodots rule with polymolecularity of stating according to claim 1 is modified is characterized in that the described preparation method who contains sulfydryl De perylene diimide derivative molecular may further comprise the 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
2Protection is down 100～150 ℃ of stirring reactions 3～12 hours;
2) reaction soln is joined in the absolute ethyl alcohol of 500～1000 mL precipitate, filter and collect filter residue, it is 5～10% sodium hydroxide solution washing 3～5 times that filter residue uses weight percent concentration again, filter, until filtrating for colourless;
3) filter residue becomes neutral with the pH value of deionized water wash to filtrating, and is dry in 70 ℃ of vacuum drying ovens, obtains containing the perylene diimide derivative molecular of sulfydryl.
4. the graphene film matrix material of modifying according to the said a kind of metallic nanodots rule with polymolecularity of claim 1 is characterized in that said metallic nanodots is gold nano point, silver-colored nano dot, platinum nano dot or palladium nano dot.
5. the in-situ preparation method of a graphene film matrix material of modifying according to the said metallic nanodots rule with polymolecularity of claim 1 is characterized in that its step is following:
1) 2.5～5 mg contain sulfydryl De perylene diimide derivative molecular after the dissolving of 1～2 mL deionized water for ultrasonic; 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 not tolerant back in 30～60 ℃ of stirred overnight, obtains being contained the graphene oxide sheet aqueous solution that the perylene diimide derivative molecular of sulfydryl is modified;
2) contain to 10～20 mL that to add 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 in the graphene oxide sheet aqueous solution that sulfydryl De perylene diimide derivative molecular modifies be 28% ammonia soln; Rock mixing solutions after 3～5 minutes in 90～100 ℃ of stirring reactions 1～3 hour; The dark solution that obtains is to contain the graphene film aqueous solution that sulfydryl De perylene diimide derivative molecular is modified, in the product excessive Hydrazine Hydrate 80 with contain sulfydryl De perylene diimide derivative molecular and remove through the dialysis of 3500～5000 molecular weight dialysis tubings;
3) 1～5 mL, 0.1 mg/mL Thiovanic acid joins in the graphene film aqueous solution of 5～25 mL thiol molecule modification; Under agitation add 0.16～0.8 mL, 10 mM aqueous metal salts continuation reaction and spend the night, obtain having the regular graphene film nano composite material aqueous solution of modifying of metallic nanodots of polymolecularity.
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| CN102923700A (en) * | 2012-11-30 | 2013-02-13 | 南京大学 | Preparation method of thiol-modified graphene |
| CN104569052A (en) * | 2014-12-17 | 2015-04-29 | 东南大学 | Method for preparing graphene oxide sensor |
| CN108637270A (en) * | 2018-05-02 | 2018-10-12 | 戚明海 | A method of preparing metal nanoparticle by template of graphene oxide |
| 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 |
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| CN101913592A (en) * | 2010-08-10 | 2010-12-15 | 浙江大学 | Covalent functionalization graphene and preparation method thereof |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
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| WO2009143405A2 (en) * | 2008-05-22 | 2009-11-26 | The University Of North Carolina At Chapel Hill | Synthesis of graphene sheets and nanoparticle composites comprising same |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
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| CN102923700B (en) * | 2012-11-30 | 2015-05-20 | 南京大学 | Preparation method of thiol-modified graphene |
| CN104569052A (en) * | 2014-12-17 | 2015-04-29 | 东南大学 | Method for preparing graphene oxide sensor |
| CN104569052B (en) * | 2014-12-17 | 2017-02-22 | 东南大学 | Method for preparing graphene oxide sensor |
| CN108637270A (en) * | 2018-05-02 | 2018-10-12 | 戚明海 | A method of preparing metal nanoparticle by template of graphene oxide |
| 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 |
| CN110229153A (en) * | 2019-06-24 | 2019-09-13 | 赣南师范大学 | A kind of intercalated molecule and preparation method thereof, two-dimensional nano composite material |
| CN110274936A (en) * | 2019-07-09 | 2019-09-24 | 济南大学 | For detecting the organo-mineral complexing film and gas sensor of triethylamine |
| CN110274936B (en) * | 2019-07-09 | 2021-10-26 | 济南大学 | Organic-inorganic composite film for detecting triethylamine and gas sensor |
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