JP2008169091A - Carbon nanotube coated uniformly with ultrathin nanoprecision polypyrrole layer - Google Patents
Carbon nanotube coated uniformly with ultrathin nanoprecision polypyrrole layer Download PDFInfo
- Publication number
- JP2008169091A JP2008169091A JP2007004956A JP2007004956A JP2008169091A JP 2008169091 A JP2008169091 A JP 2008169091A JP 2007004956 A JP2007004956 A JP 2007004956A JP 2007004956 A JP2007004956 A JP 2007004956A JP 2008169091 A JP2008169091 A JP 2008169091A
- Authority
- JP
- Japan
- Prior art keywords
- polypyrrole
- carbon nanotubes
- coated
- carbon nanotube
- ultrathin
- 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.)
- Granted
Links
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 50
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 49
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 46
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 239000008213 purified water Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 abstract description 8
- 239000002071 nanotube Substances 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000002048 multi walled nanotube Substances 0.000 description 32
- 239000010408 film Substances 0.000 description 25
- 239000002070 nanowire Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BOPGDPNILDQYTO-NNYOXOHSSA-N nicotinamide-adenine dinucleotide Chemical compound C1=CCC(C(=O)N)=CN1[C@H]1[C@H](O)[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OC[C@@H]2[C@H]([C@@H](O)[C@@H](O2)N2C3=NC=NC(N)=C3N=C2)O)O1 BOPGDPNILDQYTO-NNYOXOHSSA-N 0.000 description 2
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Abstract
Description
本発明は、ナノバイオセンサ、ナノエレクトロニクス・デバイス、電池、等々の分野で有益に使用されるであろう「ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブ」に関するものである。本発明は、また、このナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブの製造方法にも関する。 The present invention relates to “carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin films” that may be beneficially used in the fields of nanobiosensors, nanoelectronic devices, batteries, and the like. The present invention also relates to a method for producing carbon nanotubes uniformly coated with the nano-precision polypyrrole ultrathin film.
カーボンナノチューブとポリマーに基づく複合材料は、これら複合材料を構成する各要素よりも優れた特性をもつ進化した機能性材料を創出すると期待される理由から、多くの興味が持たれてきた(M.J.Panhuis, 2006; C.Downs et al, 1999)。カーボンナノチューブ／ポリマー複合材料は、ポリマーの導電性を改善し、それらの強靭性を増強させ、あるいはバイオ分子を固定化するために調製されてきた(A.Merkoci et al, 2005)。支えなしに立つ個々の非導電性ポリマの鞘でコートされたカーボンナノチューブは、ＡＦＭ絶縁チップとして(M.J.Esplandiu et al, 2004)、ナノ電極(J.K.Champbell et al, 1999)として、あるいはナノエレクトロニクス・デバイス用ナノワイヤ(A.Star et al, 2003; G.B.Blanchet et al, 2004)として用いられてきた。 Composite materials based on carbon nanotubes and polymers have received a lot of interest because they are expected to create advanced functional materials with properties superior to the components that make up these composite materials (MJPanhuis , 2006; C. Downs et al, 1999). Carbon nanotube / polymer composites have been prepared to improve the conductivity of polymers, enhance their toughness, or immobilize biomolecules (A.Merkoci et al, 2005). Carbon nanotubes coated with freestanding individual non-conductive polymer sheaths can be used as AFM insulating tips (MJEsplandiu et al, 2004), as nanoelectrodes (JKChampbell et al, 1999), or as nanoelectronic devices Nanowires (A. Star et al, 2003; GBBlanchet et al, 2004) have been used.
特に興味深いのは、ポリピロール、ポリアニリンあるいはポリチオフェンのような導電性機能を有するポリマーと複合させたカーボンナノチューブ（ＣＮＴ）の性質である(M.J.Panhuis, 2006)。カーボンナノチューブを導電性ポリマーによって化学的又は電気化学的に被覆する研究は、いくつかのグループで検討されてきたけれども、支えなしに立つ個々のカーボンナノチューブをポリマーでナノサイズに精確に均一厚みに被覆することは、未だ達成されていない魅力的な課題として残されてきた。何故ならば、結合させるポリマーの凝集を制御することは容易ではなく、また、そのポリマー鎖は不規則的なナノ粒子又は沈殿物として堆積しやすいからである。カーボンナノチューブはしばしばポリピロールの凝集物に取り込まれることがあり(J.Wang et al, 2005)、あるいは、５０ｎｍ（非特許文献１、２参照）から８０ｎｍ（J.Fan et al, 1999; J.H.Chen et al, 2001; J.H.Chen et al, 2002）の厚み範囲の非均一のポリマー層で被覆されることがあり、また、ポリマー構造の中にしばしば一以上のカーボンナノチューブ（前記非特許文献２参照）が包み込まれることもあり、更には、径が約５０ｎｍのポリピロールナノ粒子で被覆されることもある(Y.Yu et al, 2005; T.-M. Wu et al, 2006)からである。
しかし、ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブを製造する方法は未だ知られていない。
Of particular interest is the nature of carbon nanotubes (CNTs) complexed with polymers with conductive function such as polypyrrole, polyaniline or polythiophene (MJPanhuis, 2006). Although studies of chemically or electrochemically coating carbon nanotubes with conducting polymers have been studied by several groups, individual carbon nanotubes that stand unsupported can be coated with a polymer to a nano-size precisely and uniformly in thickness. To do has been left as an attractive challenge that has not yet been achieved. This is because it is not easy to control the aggregation of the polymer to be bonded, and the polymer chains are likely to deposit as irregular nanoparticles or precipitates. Carbon nanotubes are often incorporated into polypyrrole aggregates (J. Wang et al, 2005), or 50 nm (see Non-Patent Documents 1 and 2) to 80 nm (J. Fan et al, 1999; JHChen et al , 2001; JHChen et al, 2002) and may be coated with a non-uniform polymer layer in the thickness range, and often contain one or more carbon nanotubes (see Non-Patent Document 2) in the polymer structure. In some cases, it may be coated with polypyrrole nanoparticles having a diameter of about 50 nm (Y. Yu et al, 2005; T.-M. Wu et al, 2006).
However, a method for producing carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin film is not yet known.
本発明の目的は、ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブを提供することであり、また、そのようなポリピロール層で被覆されているカーボンナノチューブの製造方法を提供することである。 An object of the present invention is to provide a carbon nanotube uniformly coated with a nano-precision polypyrrole ultrathin film, and also to provide a method for producing a carbon nanotube coated with such a polypyrrole layer. is there.
〔発明の概要〕
上記目的を達成するため、本発明者らは前駆体（モノマー）としてピロールを用いてカーボンナノチューブを被覆することを試みた。幅広い濃度のピロールと幾つかの機能化カーボンナノチューブを試み、そして、ピロールの濃度は非常に低い濃度（ｍＭのレベル）にするべきであることを掴んで、本発明を完成するに至った。
[Summary of the Invention]
In order to achieve the above object, the present inventors tried to coat carbon nanotubes using pyrrole as a precursor (monomer). A wide range of concentrations of pyrrole and some functionalized carbon nanotubes were tried, and the pyrrole concentration should be very low (in the order of mM) to complete the present invention.
第一に、本発明は、ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブを提供する。 First, the present invention provides a carbon nanotube uniformly coated with a nano-precision polypyrrole ultrathin film.
第二に、本発明は、上記ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブの製造方法であって、次の工程を含むものである。
（ｉ）カーボンナノチューブを濃硝酸中、高温条件下に処理して機能化する；
（ii）得られた機能化カーボンナノチューブ（ＣＮＴｏｘ）を所定濃度となるように精製水に分散する。
（iii）２−プロパノールに溶かしたピロールを、所定のピロール濃度に達するまで加え、続いて過硫酸塩を加え、これを混合する；
（iｖ）得られた個々のポリピロール被覆カーボンナノチューブ（固体）を分離し、乾燥する。
Secondly, the present invention is a method for producing a carbon nanotube uniformly coated with the nano-precision polypyrrole ultrathin film, and includes the following steps.
(I) functionalizing carbon nanotubes by treating them in concentrated nitric acid under high temperature conditions;
(Ii) The obtained functionalized carbon nanotube (CNTox) is dispersed in purified water so as to have a predetermined concentration.
(Iii) Add pyrrole dissolved in 2-propanol until a predetermined pyrrole concentration is reached, then add persulfate and mix it;
(Iv) The obtained individual polypyrrole-coated carbon nanotubes (solid) are separated and dried.
＜略語＞
略語は、本明細書では、次の意味をもつ。
・ＣＮＴ：カーボンナノチューブ
・ＣＮＴｏｘ：酸化型（機能化）カーボンナノチューブ
・ＳＷＣＮＴ：単層（ｓｉｎｇｌｅ−ｗａｌｌｅｄ）カーボンナノチューブ
・ＭＷＣＮＴ：多層（ｍｕｌｔｉｗａｌｌｅｄ）カーボンナノチューブ
・ＭＷＣＮＴｏｘ：酸化型（機能化）多層（ｍｕｌｔｉｗａｌｌｅｄ）カーボンナノチューブ
・Ｐｙ：ピロール
・ＰＰｙ：ポリピロール
<Abbreviation>
Abbreviations have the following meanings herein.
・ CNT: Carbon nanotube
CNTox: oxidized (functionalized) carbon nanotubes SWCNT: single-walled carbon nanotubes MWCNT: multiwalled carbon nanotubes MWCNTox: oxidized (functionalized) multiwalled carbon nanotubes Py: Pyrrole / PPy: Polypyrrole
本発明の、ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブは、ナノエレクトロニクス・デバイスに扉を開くものである。
本発明の製造方法は、簡単で、（被覆層の厚みを）変えられる化学的方法である。それゆえ、これにより、ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブを容易に製造できる。
The carbon nanotubes of the present invention uniformly coated with nano-precision polypyrrole ultrathin films open the door to nanoelectronic devices.
The production method of the present invention is a chemical method that is simple and can change the thickness of the coating layer. Therefore, this makes it possible to easily produce carbon nanotubes that are uniformly coated with nano-precision polypyrrole ultrathin films.
〔発明の更に詳しい説明〕
次に、添付図面を参照しながら、本発明を更に詳しく説明する。
図１は、カーボンナノチューブの上にポリピロール超薄膜を均一に被覆する模式図を示す。
この方法で用いるカーボンナノチューブは、炭素の異型（allotype）の一つである。これは、その直径が２ｎｍ〜１００ｎｍの柱状分子の形態を有しており、グラファイト・シートを丸めた形状をしている。カーボンナノチューブとして、単層カーボンナノチューブも多層カーボンナノチューブもいずれも使用できるが、好ましくは多層カーボンナノチューブである。
この方法の工程（ｉ）における「機能化する（させる）」とは、カーボンナノチューブの外側のグラファイト・シートにカルボキシル基を導入することを意味する。
この方法の工程（ｉ）における「高温」とは、７０℃ないしは９０℃の範囲中の一定温度に維持することを意味する。また、その高温処理は反応が終わるまで、例えば、１２〜３６ｈ行なわれる。
この方法の工程（ｉｉ）における「ＣＮＴｏｘの所定濃度」とは、０．１−１．０ｍｇ／ｍＬの濃度を意味する。
この方法の工程（ｉｉｉ）における「所定のピロール濃度」とは、ピロールを５ｍＭと２５ｍＭ（この濃度は最終ポリピロール被覆層の要求厚みに依存するが）の間にある一定濃度に維持すること意味する。
＜その他＞
２−プロパノールを用いる理由は、前駆体のピロール溶液を安定に維持するためである。過硫酸塩を用いる理由は、過硫酸塩がピロールのラジカル・ポリメリゼーションを開始させるからである。
[Detailed description of the invention]
Next, the present invention will be described in more detail with reference to the accompanying drawings.
FIG. 1 shows a schematic view of uniformly coating a polypyrrole ultrathin film on a carbon nanotube.
The carbon nanotube used in this method is one of carbon allotypes. This has a form of a columnar molecule having a diameter of 2 nm to 100 nm, and is formed by rounding a graphite sheet. As the carbon nanotube, both single-walled carbon nanotubes and multi-walled carbon nanotubes can be used, but multi-walled carbon nanotubes are preferable.
“Functionalize” in step (i) of this method means introducing a carboxyl group into the graphite sheet outside the carbon nanotube.
“High temperature” in step (i) of this method means maintaining at a constant temperature in the range of 70 ° C. or 90 ° C. Further, the high temperature treatment is performed, for example, for 12 to 36 hours until the reaction is completed.
The “predetermined concentration of CNTox” in step (ii) of this method means a concentration of 0.1 to 1.0 mg / mL.
“Predetermined pyrrole concentration” in step (iii) of this method means that pyrrole is maintained at a constant concentration between 5 mM and 25 mM (although this concentration depends on the required thickness of the final polypyrrole coating). .
<Others>
The reason for using 2-propanol is to keep the precursor pyrrole solution stable. The reason for using persulfate is that persulfate initiates radical polymerization of pyrrole.
本発明によれば、ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブを得ることができる。
ここで、「ナノ精度のポリピロール超薄膜で均一に」とは、通常、５ｎｍないしは２０ｎｍ（好ましくは７ｎｍないしは１４ｎｍであり、これはピロールモノマーの厚みが０．４３ｎｍであることを考慮すると、１６分子ないしは３２分子に相当するピロールモノマーが積み重なった厚み）の範囲の中の所定厚み（これはピロール前駆体の濃度に依存するが）でその偏差が１ｎｍ以下、又は変動係数が２０％以下（好ましくは１６％以下、更に好ましくは１１％以下）の連続的なポリピロール層を意味する。
According to the present invention, it is possible to obtain carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin films.
Here, “uniformly with nano-precision polypyrrole ultrathin film” usually means 5 nm to 20 nm (preferably 7 nm to 14 nm, which is 16 molecules considering the thickness of the pyrrole monomer is 0.43 nm. Or a predetermined thickness within the range of pyrrole monomers corresponding to 32 molecules (which depends on the concentration of the pyrrole precursor), the deviation is 1 nm or less, or the variation coefficient is 20% or less (preferably 16% or less, more preferably 11% or less) means a continuous polypyrrole layer.
実施例１ ナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブの調製
（１）調製方法
コーティング：多層カーボンナノチューブは、濃硝酸（６Ｍ）中、８０℃で、２４ｈ処理し、機能化した。引き続いて、酸／多層ＣＮＴ混合物は蒸留水で洗浄し、水溶液が中性ｐＨとなるまで数回、遠沈した。引き続き、カルボキシル基含有の機能化された多層カーボンナノチューブ（ＭＷＣＮＴｏｘ）を孔径０．２μｍのメンブランフィルター（Nuclepore Track-Etch Membrane, Whatman, UK）に掛け、室温で乾燥させた。ポリピロールを被覆する工程では、ＭＷＣＮＴｏｘを蒸留水中に０．５ｍｇ／ｍＬの濃度となるように分散させ（典型的には、ＭＷＣＮＴｏｘの２ｇを蒸留水４ｍＬに分散させ）、つづいて超音波処理を５分間行なった。引き続いて、ピロールの２−プロパノール溶液を加えピロール最終濃度を所定濃度（典型的には１０ｍＭで、２−プロパノールに溶かした４５１ｍＭピロール保存溶液を１００μＬ加えることが必要。）とし、更に過硫酸アンモニウム（典型的には、１０ｍＭ過硫酸アンモニウム保存水溶液４１０μＬ）を加えた。この混合物を、マグネチックスターラ（５５０ｒｐｍ）を用いて２４ｈかき混ぜ、最後に、孔径０．２μｍのNucleporeメンブランフィルターに掛け、蒸留水で洗い、室温で乾燥した。
Example 1 Preparation of carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin film (1) Preparation method Coating: Multi-walled carbon nanotubes were treated in concentrated nitric acid (6M) at 80 ° C. for 24 h to be functionalized . Subsequently, the acid / multilayer CNT mixture was washed with distilled water and spun down several times until the aqueous solution had a neutral pH. Subsequently, the functionalized multi-wall carbon nanotubes (MWCNTox) containing carboxyl groups were passed through a membrane filter (Nuclepore Track-Etch Membrane, Whatman, UK) having a pore size of 0.2 μm and dried at room temperature. In the step of coating polypyrrole, MWCNTox is dispersed in distilled water to a concentration of 0.5 mg / mL (typically 2 g of MWCNTox is dispersed in 4 mL of distilled water), followed by ultrasonic treatment. For a minute. Subsequently, a 2-propanol solution of pyrrole is added to give a final pyrrole concentration (typically 10 mM, and it is necessary to add 100 μL of a 451 mM pyrrole stock solution dissolved in 2-propanol), and ammonium persulfate (typically Specifically, 10 mM ammonium persulfate stock aqueous solution 410 μL) was added. This mixture was stirred for 24 h using a magnetic stirrer (550 rpm), finally passed through a Nuclepore membrane filter with a pore size of 0.2 μm, washed with distilled water, and dried at room temperature.
（２）特性評価
得られたナノ精度のポリピロール超薄膜で均一に被覆されているカーボンナノチューブは、次の手法、すなわち、透過型電子顕微鏡、走査型電子顕微鏡、ラーマン分光法、Ｘ線光電子分光法、電子エネルギー損失分光法及びエレクトロケミストリーを用いて、特性評価をした。
(2) Characteristic evaluation The carbon nanotubes uniformly coated with the obtained nano-precision polypyrrole ultrathin film are obtained by the following methods: transmission electron microscope, scanning electron microscope, Raman spectroscopy, X-ray photoelectron spectroscopy. Characterization was performed using electron energy loss spectroscopy and electrochemistry.
（ａ）電子エネルギー損失分光法及びエレクトロケミストリー
ＰＰｙ／ＭＷＣＮＴの各々の元素組成は、電子エネルギー損失スペクトロスコピー（ＥＥＬＳ）によって分析した。π＊（２８３．８ｅＶ）及びσ＊（２９５．５ｅＶ）ピークが、Ｃ−Ｋ殻イオニゼーション・エッジの近くではっきりと見られた。π＊ピークは、炭素原子がｓｐ２ハイブリダイズドであり、そのカーボンチューブが主として六角形のグラファイト層から成ることを示している。我々はまた、４０１ｅＶでのイオニゼーション・エッジを観察したが、これはポリピロール被覆に存在する窒素原子に特徴的なＫエッジに対応するものである。
(A) Electron energy loss spectroscopy and electrochemistry
The elemental composition of each PPy / MWCNT was analyzed by electron energy loss spectroscopy (EELS). The π * (283.8 eV) and σ * (295.5 eV) peaks were clearly seen near the CK shell ionization edge. The π * peak indicates that the carbon atom is sp 2 hybridized and that the carbon tube consists mainly of a hexagonal graphite layer. We also observed an ionization edge at 401 eV, which corresponds to the K edge characteristic of nitrogen atoms present in the polypyrrole coating.
（ｂ）Ｘ線光電子分光法
サンプル全体についてＭＷＣＮＴのポリピロール被覆の存在を確かめ、その定量を行なうために、ＰＰｙ／ＭＷＣＮＴ及び（機能化）ＭＷＣＮＴｏｘについてＸ線光電子分光法（ＸＰＳ）測定を行なった。被覆されたＰＰｙ／ＭＷＣＮＴ及び（機能化）ＭＷＣＮＴｏｘについての広範なＸＰＳスキャンに基づくＸ線光電子スペクトルの積分による元素分析は、炭素が９４．６％、窒素が５．４％であることを示している。
(B) X-ray photoelectron spectroscopy
X-ray photoelectron spectroscopy (XPS) measurements were performed on PPy / MWCNT and (functionalized) MWCNTox to confirm the presence of MWCNT polypyrrole coating on the entire sample and to quantify it. Elemental analysis by integration of X-ray photoelectron spectra based on extensive XPS scans for coated PPy / MWCNT and (functionalized) MWCNTox shows 94.6% carbon and 5.4% nitrogen Yes.
（ｃ）ラーマン分光法
被覆されたポリピロールの存在を更に確認するために、ナノ被覆ＰＰｙ／ＭＷＣＮＴについての約１３５０ｃｍ−１付近の幅広いピークのラーマン・スペクトルを示すが、これはポリピロール環の１３３０ｃｍ−１及び１３７０ｃｍ−１の伸縮を反映しているものである。
(C) Raman spectroscopy To further confirm the presence of the coated polypyrrole, a broad peak Raman spectrum around 1350 cm −1 for nanocoated PPy / MWCNT is shown, which is 1330 cm −1 of the polypyrrole ring. And 1370 cm −1 of the expansion and contraction.
（ｄ）透過型電子顕微鏡
ピロール前駆体の濃度が１０ｍＭであったときに、形成されたポリピロール層は均一厚み７．４ｎｍ（厚みの変動係数は１１％）であり、サンプル中に観察されたＭＷＣＮＴは全てポリピロール超薄膜の鞘で覆われていた。図２は、均一厚みのポリピロール超薄膜で被覆されたカーボンナノチューブのＴＥＭ写真である。
(D) Transmission electron microscope When the concentration of the pyrrole precursor was 10 mM, the formed polypyrrole layer had a uniform thickness of 7.4 nm (thickness variation coefficient of 11%), and the MWCNT observed in the sample All were covered with an ultra-thin polypyrrole sheath. FIG. 2 is a TEM photograph of carbon nanotubes coated with an ultrathin polypyrrole film having a uniform thickness.
（ｅ）エレクトロケミストリー
ＰＰｙ／ＭＷＣＮＴナノワイヤの電気化学的挙動を観察するために、ＰＰｙ／ＭＷＣＮＴ及び（機能化）ＭＷＣＮＴｏｘの膜電極についてのサイクリック・ボルタモグラムを１Ｍ塩化ナトリウム中で記録した。ＰＰｙ／ＭＷＣＮＴナノワイヤで改変した電極の電気化学的挙動は、（機能化）ＭＷＣＮＴｏｘで被覆した電極の挙動とは著しく異なっている。ＰＰｙ／ＭＷＣＮＴナノワイヤ膜のボルタモグラムは、ポリピロール超薄膜で被覆されたＭＷＣＮＴへのＣｌ−取込みと組み合わさって、＋８ｍＶの電位で鋭い酸化ピークを示している（機能化ＭＷＣＮＴｏｘ膜は、このような応答がないことに注意）。酸化に対するこの鋭い応答は、ＭＷＣＮＴのポリピロール超薄膜の被覆において迅速かつよく分かった物質移動に帰することができる。ＭＷＣＮＴのポリピロール被覆に関し更に情報を得るために、我々はＭＷＣＮＴｏｘ及びＰＰｙ／ＭＷＣＮＴナノワイヤで改変した電極のキャパシタンスを計算した。これは、＋０．４０Ｖ（銀／塩化銀電極に対し）の電圧で記録された電流を、５０ｍＭリン酸緩衝液（ｐＨが７．４；スキャン範囲が毎秒約２００ｍＶ〜１１００ｍＶ）中におけるサイクリック・ボルタメトリー実験のあいだに、スキャン速度を変化（毎秒２５ｍＶ〜２００ｍＶの範囲）させ、その結果をプロットすることで測定した。これらのプロットはいずれの場合も直線的であり、そのことは基準電流は静電容量の充電／放電の電流に直接的に呼応していることを示している。機能化ＭＷＣＮＴｏｘ及びＰＰｙ／ＭＷＣＮＴ膜の表面特異的キャパシタンスは、各々、１．９２μＦｍｍ−２及び１．５３μＦｍｍ−２（一方、むき出しＧＣ電極のキャパシタンスは１．３１μＦｍｍ−２であった）であり、これは１Ｍ塩化ナトリウム溶液における機能化ＭＷＣＮＴ及びＰＰｙ／ＭＷＣＮＴ膜のボルタメトリック挙動と整合している。
(E) Electrochemistry
To observe the electrochemical behavior of PPy / MWCNT nanowires, cyclic voltammograms for PPy / MWCNT and (functionalized) MWCNTox membrane electrodes were recorded in 1M sodium chloride. The electrochemical behavior of electrodes modified with PPy / MWCNT nanowires is significantly different from that of electrodes functionalized with (functionalized) MWCNTox. The voltammograms of PPy / MWCNT nanowire films show a sharp oxidation peak at a potential of +8 mV combined with Cl - uptake into MWCNTs coated with ultrathin polypyrrole films (functionalized MWCNTox films exhibit such a response. Note that there is no). This sharp response to oxidation can be attributed to rapid and well-known mass transfer in the coating of MWCNT polypyrrole ultrathin films. To obtain more information about the polypyrrole coating of MWCNT, we calculated the capacitance of the electrode modified with MWCNTox and PPy / MWCNT nanowires. This is because the current recorded at a voltage of +0.40 V (relative to the silver / silver chloride electrode) is cyclically measured in a 50 mM phosphate buffer (pH 7.4; scan range about 200 mV to 1100 mV per second). During the voltammetry experiment, the scan speed was varied (range 25 mV to 200 mV per second) and the results were plotted. These plots are linear in each case, which indicates that the reference current is directly responsive to the capacitance charge / discharge current. The surface specific capacitances of the functionalized MWCNTox and PPy / MWCNT films are 1.92 μFmm −2 and 1.53 μFmm −2 (while the capacitance of the bare GC electrode was 1.31 μFmm −2 ), respectively. Is consistent with the voltammetric behavior of functionalized MWCNT and PPy / MWCNT films in 1M sodium chloride solution.
次に、我々はＰＰｙ／ＭＷＣＮＴナノワイヤの電気化学的性状に及ぼすポリピロールのナノ被覆の影響を検討した。フェリシアナイドが機能化ＭＷＣＮＴｏｘに対してもＰＰｙ／ＭＷＣＮＴナノワイヤ膜に対しても可逆的応答を示した一方で、ＰＰｙ／ＭＷＣＮＴナノワイヤ膜では、より鋭いピーク及びより低いΔＥpが観察された（ΔＥpはＰＰｙ／ＭＷＣＮＴナノワイヤ膜で４６４ｍＶ、機能化ＭＷＣＮＴｏｘ膜で５０２ｍＶ）。ＮＡＤＨに対するサイクリック・ボルタメトリック実験によれば、機能化ＭＷＣＮＴｏｘ膜に比べＰＰｙ／ＭＷＣＮＴナノワイヤ膜のほうが、このＮＡＤＨ分子の酸化に対する電気化学的反応性が改善されることを示している（酸化ピーク電位は、各々、６８４ｍＶ及び７１０ｍＶであり、酸化ピーク電流は、各々、２９．１μＡ及び２６．５μＡである）。過酸化水素に対するサイクリック・ボルタメトリック応答によれば、機能化ＭＷＣＮＴｏｘでは過酸化水素の酸化が＋６５０ｍＶで開始するが、一方、ＰＰｙ／ＭＷＣＮＴでは過酸化水素の酸化がこれよりも低い＋５００ｍＶで開始することを示している。これらの結果は、ポリピロールナノ被覆ＭＷＣＮＴは、裸の機能化ＭＷＣＮＴｏｘに比べて改善された電気化学的性状を有することを示すものである。したがって、今後、このナノ構造のポリピロール層被覆ＭＷＣＮＴは電気化学的センサー等として、非常に有望な特徴を有する材料となるであろう。 Next, we investigated the effect of polypyrrole nano-coating on the electrochemical properties of PPy / MWCNT nanowires. While ferricyanide showed a reversible response to both functionalized MWCNTox and PPy / MWCNT nanowire films, sharper peaks and lower ΔEp were observed in PPy / MWCNT nanowire films (ΔEp is 464 mV for PPy / MWCNT nanowire membranes and 502 mV for functionalized MWCNTox membranes). Cyclic voltammetric experiments on NADH show that the PPy / MWCNT nanowire film has improved electrochemical reactivity to oxidation of this NADH molecule compared to the functionalized MWCNTox film (oxidation peak potential). Are 684 mV and 710 mV, respectively, and the oxidation peak currents are 29.1 μA and 26.5 μA, respectively). According to the cyclic voltammetric response to hydrogen peroxide, functionalized MWCNTox begins to oxidize hydrogen peroxide at +650 mV, whereas PPy / MWCNT begins to oxidize hydrogen peroxide at +500 mV, which is lower than this. It is shown that. These results indicate that polypyrrole nanocoated MWCNTs have improved electrochemical properties compared to bare functionalized MWCNTox. Therefore, in the future, this nano-structured polypyrrole layer-coated MWCNT will be a material having very promising characteristics as an electrochemical sensor or the like.
実施例２ ピロール濃度とポリピロール層の厚みとの関係
ピロール濃度を１０ｍＭ、１５ｍＭ及び２０ｍＭに変化させたほかは、実施例１と同様にして、ポリピロール被覆カーボンナノチューブを調製した。得られたポリピロール被覆カーボンナノチューブのＴＥＭ観察結果を表１にまとめた。
Claims (3)
（ｉ）カーボンナノチューブを濃硝酸中、高温条件下に処理して機能化する；
（ii）得られた機能化カーボンナノチューブ（ＣＮＴｏｘ）を所定濃度となるように精製水に分散する。
（iii）２−プロパノールに溶かしたピロールを、所定のピロール濃度に達するまで加え、続いて過硫酸塩を加え、これを混合する；
（iｖ）得られた個々のポリピロール被覆カーボンナノチューブ（固体）を分離し、乾燥する。 A method for producing a carbon nanotube uniformly coated with the above-described nano-precision polypyrrole ultrathin film, comprising the following steps.
(I) functionalizing carbon nanotubes by treating them in concentrated nitric acid under high temperature conditions;
(Ii) The obtained functionalized carbon nanotube (CNTox) is dispersed in purified water so as to have a predetermined concentration.
(Iii) Add pyrrole dissolved in 2-propanol until a predetermined pyrrole concentration is reached, then add persulfate and mix it;
(Iv) The obtained individual polypyrrole-coated carbon nanotubes (solid) are separated and dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007004956A JP5224434B2 (en) | 2007-01-12 | 2007-01-12 | Carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007004956A JP5224434B2 (en) | 2007-01-12 | 2007-01-12 | Carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008169091A true JP2008169091A (en) | 2008-07-24 |
| JP5224434B2 JP5224434B2 (en) | 2013-07-03 |
Family
ID=39697543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007004956A Active JP5224434B2 (en) | 2007-01-12 | 2007-01-12 | Carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5224434B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103196969A (en) * | 2013-04-08 | 2013-07-10 | 天津大学 | Method for dispersing carbon nanotubes by aspartame, and application electrode |
| CN103399052A (en) * | 2013-08-02 | 2013-11-20 | 嘉兴学院 | Molecularly imprinted electrochemical sensor and preparation method thereof |
| JP2014101234A (en) * | 2012-11-16 | 2014-06-05 | Asahi Kasei Chemicals Corp | Surface-treated carbon nanotube |
| JP2014101233A (en) * | 2012-11-16 | 2014-06-05 | Asahi Kasei Chemicals Corp | Surface-treated carbon nanotube |
| CN110452420A (en) * | 2019-08-26 | 2019-11-15 | 徐州杰卡诺智能科技有限公司 | A kind of carbon nano tube surface method of modifying and the method for preparing composite plastic using it |
| CN113228352A (en) * | 2019-05-31 | 2021-08-06 | 株式会社Lg化学 | Carbon having polymer layer containing redox functional group formed thereon, and sulfur-carbon composite and lithium secondary battery comprising the same |
| CN114293365A (en) * | 2021-09-09 | 2022-04-08 | 深圳大学 | Preparation method of wet-voltage power generation material and wet-voltage power generation material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008032071A1 (en) * | 2006-09-13 | 2008-03-20 | University Of Nottingham | Polymer - carbon nanotube composites |
-
2007
- 2007-01-12 JP JP2007004956A patent/JP5224434B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008032071A1 (en) * | 2006-09-13 | 2008-03-20 | University Of Nottingham | Polymer - carbon nanotube composites |
Non-Patent Citations (4)
| Title |
|---|
| JPN6012041732; ＷＵ，Ｔ． ｅｔ ａｌ: 'Ｓｙｎｔｈｅｓｉｓ， Ｃｈａｒａｃｔｅｒｉｚａｔｉｏｎ， ａｎｄ Ｅｌｅｃｔｒｉｃａｌ Ｐｒｏｐｅｒｔｉｅｓ ｏｆ Ｐｏｌｙｐｙｒｒｏｌｅ／Ｍｕｌｔｉｗａｌｌｅｄ Ｃａｒｂｏｎ Ｎａｎｏｔｕｂｅ Ｃｏ' Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ． Ｐａｒｔ Ａ． Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ Ｖｏｌ．４４, 20061101, ｐ．６４４９-６４５７ * |
| JPN6012041734; ＣＨＥＮ，Ｇ．Ｚ． ｅｔ ａｌ: 'Ｃａｒｂｏｎ Ｎａｎｏｔｕｂｅ ａｎｄ Ｐｏｌｙｐｙｒｒｏｌｅ Ｃｏｍｐｏｓｉｔｅｓ： Ｃｏａｔｉｎｇ ａｎｄ Ｄｏｐｉｎｇ．' ＡＤＶＡＮＣＥＤ ＭＡＴＥＲＩＡＬＳ Ｖｏｌ．１２， Ｎｏ．７, 2000, ｐ．５２２-５２６ * |
| JPN6012041735; ＪＡＮＧ，Ｊ． ｅｔ ａｌ: 'Ａ ｆａｃｉｌｅ ｓｙｎｔｈｅｓｉｓ ｏｆ ｐｏｌｙｐｙｒｒｏｌｅ ｎａｎｏｔｕｂｅｓ ｕｓｉｎｇ ａ ｔｅｍｐｌａｔｅ-ｍｅｄｉａｔｅｄ ｖａｐｏｒ ｄｅｐｏｓｉｔｉｏｎ ｐｏｌｙｍｅｒｉｚａｔｉｏ' Ｃｈｅｍｉｃａｌ Ｃｏｍｍｕｎｉｃａｔｉｏｎｓ Ｎｏ．７, 2004, ｐ．８８２-８８３ * |
| JPN6012041737; ＺＨＡＮＧ，Ｘ． ｅｔ ａｌ: 'Ｓｉｎｇｌｅ-Ｗａｌｌｅｄ Ｃａｒｂｏｎ Ｎａｎｏｔｕｂｅ-Ｂａｓｅｄ Ｃｏａｘｉａｌ Ｎａｎｏｗｉｒｅｓ： Ｓｙｎｔｈｅｓｉｓ， Ｃｈａｒａｃｔｅｒｉｚａｔｉｏｎ， ａｎｄ Ｅｌｅｃｔｒｉｃａｌ Ｐ' Ｊｏｕｒｎａｌ ｏｆ Ｐｈｙｓｉｃａｌ Ｃｈｅｍｉｓｔｒｙ Ｂ Ｖｏｌ．１０９， Ｎｏ．３, 2005, ｐ．１１０１-１１０７ * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014101234A (en) * | 2012-11-16 | 2014-06-05 | Asahi Kasei Chemicals Corp | Surface-treated carbon nanotube |
| JP2014101233A (en) * | 2012-11-16 | 2014-06-05 | Asahi Kasei Chemicals Corp | Surface-treated carbon nanotube |
| CN103196969A (en) * | 2013-04-08 | 2013-07-10 | 天津大学 | Method for dispersing carbon nanotubes by aspartame, and application electrode |
| CN103399052A (en) * | 2013-08-02 | 2013-11-20 | 嘉兴学院 | Molecularly imprinted electrochemical sensor and preparation method thereof |
| CN103399052B (en) * | 2013-08-02 | 2016-07-06 | 嘉兴学院 | Molecular imprinting electrochemical sensor and preparation method thereof |
| CN113228352A (en) * | 2019-05-31 | 2021-08-06 | 株式会社Lg化学 | Carbon having polymer layer containing redox functional group formed thereon, and sulfur-carbon composite and lithium secondary battery comprising the same |
| EP3902053A4 (en) * | 2019-05-31 | 2022-02-23 | LG Chem, Ltd. | Carbon having redox functional group-containing polymer layer formed thereon, and sulfur-carbon composite and lithium secondary battery including same |
| CN110452420A (en) * | 2019-08-26 | 2019-11-15 | 徐州杰卡诺智能科技有限公司 | A kind of carbon nano tube surface method of modifying and the method for preparing composite plastic using it |
| CN114293365A (en) * | 2021-09-09 | 2022-04-08 | 深圳大学 | Preparation method of wet-voltage power generation material and wet-voltage power generation material |
| CN114293365B (en) * | 2021-09-09 | 2023-06-16 | 深圳大学 | Preparation method of wet-voltage power generation material and wet-voltage power generation material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5224434B2 (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | A promising sensing platform toward dopamine using MnO2 nanowires/electro-reduced graphene oxide composites | |
| Lorestani et al. | One-step hydrothermal green synthesis of silver nanoparticle-carbon nanotube reduced-graphene oxide composite and its application as hydrogen peroxide sensor | |
| Dağcı et al. | Preparation of free-standing and flexible graphene/Ag nanoparticles/poly (pyronin Y) hybrid paper electrode for amperometric determination of nitrite | |
| Nia et al. | A novel non-enzymatic H2O2 sensor based on polypyrrole nanofibers–silver nanoparticles decorated reduced graphene oxide nano composites | |
| Srivastava et al. | Functionalized multilayered graphene platform for urea sensor | |
| Nia et al. | Electrodeposition of copper oxide/polypyrrole/reduced graphene oxide as a nonenzymatic glucose biosensor | |
| Karuwan et al. | Inkjet-printed graphene-poly (3, 4-ethylenedioxythiophene): poly (styrene-sulfonate) modified on screen printed carbon electrode for electrochemical sensing of salbutamol | |
| Xiao et al. | Growth of metal–metal oxide nanostructures on freestanding graphene paper for flexible biosensors | |
| Mani et al. | Iron nanoparticles decorated graphene-multiwalled carbon nanotubes nanocomposite-modified glassy carbon electrode for the sensitive determination of nitrite | |
| JP5224434B2 (en) | Carbon nanotubes uniformly coated with nano-precision polypyrrole ultrathin film | |
| Lavanya et al. | High-sensitivity ascorbic acid sensor using graphene sheet/graphene nanoribbon hybrid material as an enhanced electrochemical sensing platform | |
| Zhu et al. | Electrochemical preparation of polyaniline capped Bi2S3 nanocomposite and its application in impedimetric DNA biosensor | |
| Nguyen et al. | Development of label-free electrochemical lactose biosensor based on graphene/poly (1, 5-diaminonaphthalene) film | |
| Li et al. | Facile synthesis of 3D porous nitrogen-doped graphene as an efficient electrocatalyst for adenine sensing | |
| Azri et al. | Modification strategy of screen-printed carbon electrode with functionalized multi-walled carbon nanotube and chitosan matrix for biosensor development | |
| Shervedani et al. | Novel graphene-gold hybrid nanostructures constructed via sulfur modified graphene: Preparation and characterization by surface and electrochemical techniques | |
| Ramachandran et al. | Physiological level and selective electrochemical sensing of dopamine by a solution processable graphene and its enhanced sensing property in general | |
| Hu et al. | Carbon nanomaterials for simultaneous determination of dopamine and uric acid in the presence of ascorbic acid: from one-dimensional to the quasi one-dimensional | |
| Huang et al. | Polypyrrole-hemin-reduce graphene oxide: rapid synthesis and enhanced electrocatalytic activity towards the reduction of hydrogen peroxide | |
| Pan et al. | Hierarchical hybrid film of MnO2 nanoparticles/multi-walled fullerene nanotubes–graphene for highly selective sensing of hydrogen peroxide | |
| Yeh et al. | Electrochemical sensors for sulfamethoxazole detection based on graphene oxide/graphene layered composite on indium tin oxide substrate | |
| Kathiresan et al. | A simple one-step electrochemical deposition of bioinspired nanocomposite for the non-enzymatic detection of dopamine | |
| Tran et al. | Electrosynthesis of electrochemically reduced graphene oxide/polyaniline nanowire/silver nanoflower nanocomposite for development of a highly sensitive electrochemical DNA sensor | |
| Adekunle et al. | Electron transfer behaviour of single-walled carbon nanotubes electro-decorated with nickel and nickel oxide layers | |
| Jin et al. | Fabrication of multiwalled carbon nanotubes/polypyrrole/Prussian blue ternary composite nanofibers and their application for enzymeless hydrogen peroxide detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100112 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111220 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120821 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120905 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130305 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130307 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5224434 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160322 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160322 Year of fee payment: 3 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |