DE102006041515B4 - Process for the preparation of single or multi-walled carbon nanotubes coated with one or more transition metals - Google Patents
Process for the preparation of single or multi-walled carbon nanotubes coated with one or more transition metals Download PDFInfo
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Abstract
Verfahren zur Herstellung von ein- oder mehrwandigen, mit einem oder mehreren Übergangsmetallen beschichteten Kohlenstoff-Nanoröhren, dadurch gekennzeichnet, dass die Erzeugung der Nanoröhren und die Abscheidung der Übergangsmetalle auf den Nanoröhren mittels CVD durch Abscheidung aus der Gasphase in nur einem einzigen Prozess durchgeführt wird, indem der Precursor für die Synthese der Kohlenstoff-Nanoröhren und ein Precursor für die Beschichtung der Kohlenstoff-Nanoröhren mit Übergangsmetallen gleichzeitig ohne Prozessunterbrechung in einen Abscheidungsreaktor eingebracht werden.method for the production of single- or multi-walled, with one or more transition metals coated carbon nanotubes, characterized in that the generation of the nanotubes and the Deposition of transition metals on the nanotubes by CVD by vapor deposition in a single one Process performed is determined by the precursor for the synthesis of carbon nanotubes and a precursor for the coating the carbon nanotubes with transition metals simultaneously without process interruption in a deposition reactor be introduced.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von ein- oder mehrwandigen, mit einem oder mehreren Übergangsmetallen beschichteten Kohlenstoff-Nanoröhren.The The invention relates to a process for the production of single- or multi-walled, with one or more transition metals coated carbon nanotubes.
Verfahren zur Herstellung ein- und mehrwandiger Kohlenstoff-Nanoröhren sind allgemein bekannt und mehrfach ausführlich beschrieben [1, 2]. Es ist auch bekannt, Kohlenstoff-Nanoröhren als Supports für metallische Nanopartikel zu verwenden. Zur Herstellung solcher Nanopartikel sind verschiedene Verfahren entwickelt worden.method for producing mono- and multi-walled carbon nanotubes generally known and repeatedly described in detail [1, 2]. It is also known as carbon nanotubes as supports for metallic To use nanoparticles. For the production of such nanoparticles Various methods have been developed.
Die bisher bekannten Verfahren sind Mehrschritt-Technologien, bei denen in einem ersten Schritt die Kohlenstoff-Nanoröhren hergestellt und in einem zweiten Schritt mit Metallpartikeln beschichtet werden.The Previously known methods are multi-step technologies in which in a first step, the carbon nanotubes produced and in one second step are coated with metal particles.
Für die Herstellung von Kohlenstoff-Nanoröhren sind verschiedene Technologien bekannt.For the production of carbon nanotubes Different technologies are known.
Eines
der bekannten Verfahren ist die chemische Abscheidung aus der Gasphase
(Chemical Vapor Deposition, CVD) [2]. Dabei werden auch Metallpartikel,
z. B. mit Kohlenstoff verkapseltes Eisen, als Katalysator für die Erzeugung
der Kohlenstoff-Nanoröhren eingesetzt
(
Es
ist auch schon bekannt, Kohlenstoff-Nanoröhren in einer metallischen
Opferschicht auf einem Substrat zu erzeugen, wobei die Opferschicht
danach in einem weiteren Arbeitsschritt weggeätzt wird, so dass gleich lange
Kohlenstoff-Nanoröhren
auf dem Substrat stehen bleiben (
Für die Beschichtung von Kohlenstoff-Nanoröhren ist auch die elektrochemische Abscheidung bekannt. Bei einem dieser Verfahren werden die hergestellten Kohlenstoff-Nanoröhren mit Titan auf einem SiO2-Substrat kontaktiert. Das Titan fungiert dabei als Katode und über wässrige Lösungen von beispielsweise HAuCl4 oder K2PtCl4 oder Ag/AgCl als Referenz-Elektrode werden Au-, Pt- oder Ag-Nanopartikel auf den Kohlenstoff-Nanoröhren abgeschieden [3].For the coating of carbon nanotubes also the electrochemical deposition is known. In one of these methods, the produced carbon nanotubes are contacted with titanium on a SiO 2 substrate. The titanium acts as a cathode and Au, Pt or Ag nanoparticles are deposited on the carbon nanotubes via aqueous solutions of, for example, HAuCl 4 or K 2 PtCl 4 or Ag / AgCl as a reference electrode [3].
Bekannt ist auch die stromlose galvanische Abscheidung, bezeichnet als SEED-Verfahren, Substrate Enhanced Elektroless Deposition. Bei diesem Verfahren werden die unterschiedlich großen Redoxpotentiale der Metalle in ihren wässrigen Lösungen ausgenutzt. Zum Beispiel bei Verwendung einer Cu- Folie als Substrat und darauf fixierten Kohlenstoff-Nanoröhren, die als Kathode fungieren. Hierbei werden aus wässrigen Lösungen von Pt- und Au-Salzen Pt- und Au-Nanopartikel auf den Kohlenstoff-Nanoröhren abgeschieden, weil sie ein höheres Redox-Potential besitzen als Kupfer [4, 5].Known is also the electroless plating, referred to as SEED method, Substrate Enhanced Electroless Deposition. In this process be the different sizes Utilized redox potentials of the metals in their aqueous solutions. For example when using a Cu film as a substrate and fixed thereon Carbon nanotubes, which act as a cathode. Here are from aqueous solutions of Pt and Au salts Pt and Au nanoparticles deposited on the carbon nanotubes, because she is a higher one Have redox potential as copper [4, 5].
Eine weitere Methode Kohlenstoff-Nanoröhren mit Metallpartikeln zu beschichten besteht im Imprägnierungsverfahren. Hierbei wird in einem Mehrschrittprozess zuerst Pt-Partikel aus einer Ethylen/Glycol/H2PtCl6x 6H2O-Lösung reduziert und diese dann zusammen mit den Kohlenstoff-Nanoröhren in einer Toluol-Lösung 5 Tage unter Ultraschall behandelt [6]. Durch eine Modifizierung der Platin-Partikel mit Trimethylphosphin, was einen weiteren Zwischenschritt bedeutet, konnte die Pt-Partikel-Abscheidung auf den Nanoröhren verbessert werden.Another method to coat carbon nanotubes with metal particles is the impregnation process. In a multi-step process, Pt particles are first reduced from an ethylene / glycol / H 2 PtCl 6 x 6H 2 O solution and then sonicated for 5 days together with the carbon nanotubes in a toluene solution [6]. By modification of the platinum particles with trimethylphosphine, which represents a further intermediate step, the Pt-particle deposition on the nanotubes could be improved.
Die bisher bekannten Verfahren lassen die Herstellung von metallbeschichteten Kohlenstoff-Nanoröhren nur mit großem Aufwand durch Mehrschritt-Technologien zu.The Previously known methods allow the production of metal-coated Carbon nanotubes only with big Effort through multi-step technologies too.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung von ein- oder mehrwandigen, mit einem oder mehreren Übergangsmetallen beschichteten Kohlenstoff-Nanoröhren zu schaffen, das kostengünstig durchführbar ist und eine hohe Verfahrensausbeute gewährleistet.Of the Invention is based on the object, a process for the preparation single- or multi-walled, with one or more transition metals coated carbon nanotubes too create that cost-effectively feasible is and ensures a high process yield.
Diese Aufgabe wird mit den in den Patentansprüchen enthaltenen Merkmalen gelöst.These Task is with the features contained in the claims solved.
Erfindungsgemäß wird die Erzeugung der Nanoröhren und die Abscheidung der Übergangsmetalle auf den Nanoröhren mittels CVD durch Abscheidung aus der Gasphase in nur einem einzigen Prozess durchgeführt, indem der Precursor für die Synthese der Kohlenstoff-Nanoröhren und ein Precursor für die Beschichtung der Kohlenstoff-Nanoröhren mit Übergangsmetallen gleichzeitig ohne Prozessunterbrechung in einen Abscheidungsreaktor eingebracht werden.According to the invention, the production of the nanotubes and the deposition of the transition metals on the nanotubes by CVD by deposition from the gas phase in a single process by by introducing the precursor for the synthesis of the carbon nanotubes and a precursor for the coating of the carbon nanotubes with transition metals simultaneously in a deposition reactor without interrupting the process.
Als Precursoren für die Synthese der Kohlenstoff-Nanoröhren können nach der Erfindung Metallocene verwendet werden.When Precursors for the synthesis of the carbon nanotubes can be used according to the invention metallocenes become.
Als Precursoren für die Beschichtung der Kohlenstoff-Nanoröhren können erfindungsgemäß auch Salze oder metallorganische Verbindungen der Übergangsmetalle Kupfer, Ruthenium, Rhodium, Rhenium, Osmium, Iridium Palladium, Silber, Gold und/oder Platin verwendet werden.When Precursors for The coating of carbon nanotubes according to the invention may also be salts or organometallic compounds of the transition metals copper, ruthenium, Rhodium, rhenium, osmium, iridium palladium, silver, gold and / or Platinum can be used.
Dabei können als Salze erfindungsgemäß Halogenide, Nitrate und andere Salze der Übergangsmetalle verwendet werden. Als Halogenide können K2PtCl4 oder HAuCl4 verwendet werden und als Nitrat kann Cu(NO3)2 zur Anwendung gelangen.Halides, nitrates and other salts of the transition metals can be used as salts according to the invention. As halides K 2 PtCl 4 or HAuCl 4 can be used and as nitrate Cu (NO 3 ) 2 can be used.
Als Precursoren für die Beschichtung der Kohlenstoff-Nanoröhren können erfindungsgemäß auch Acethylacetonate und deren Derivate verwendet werden.When Precursors for According to the invention, the coating of the carbon nanotubes can also be acetylacetonates and their derivatives are used.
Als Lösungsmittel für die Precusoren können erfindungsgemäß Chloroform, Aceton, Acetonitril, Acetylaceton, m-Xylol, Kohlenstofftetrachlorid, Toluol, Benzol, Furan, Tetrahydrofuran, Pentan, Hexan, Cyclohexan, Cyclopentan, Ethanol und/oder deren Mischungen verwendet werden.When solvent for the Precursors can according to the invention chloroform, Acetone, acetonitrile, acetylacetone, m-xylene, carbon tetrachloride, Toluene, benzene, furan, tetrahydrofuran, pentane, hexane, cyclohexane, Cyclopentane, ethanol and / or mixtures thereof are used.
Der CVD-Prozess wird nach der Erfindung in einem Temperaturbereich von 700°C bis 1100°C und bei einem Druck im Bereich zwischen 10 mbar und 1,1 bar durchgeführt.Of the CVD process is according to the invention in a temperature range of 700 ° C to 1100 ° C and carried out at a pressure in the range between 10 mbar and 1.1 bar.
Die Precusoren für die Synthese der Kohlenstoff-Nanoröhren und die Precursoren für die Beschichtung mit den Übergangsmetallen können über ein Aerosol oder eine Injektion in den Abscheidungsreaktor eingebracht werden.The Precursors for the synthesis of carbon nanotubes and the precursors for the coating with the transition metals can over one Aerosol or injection introduced into the deposition reactor become.
Die Kohlenstoff-Nanoröhren werden vorteilhaft auf einem Substrat aus Si, oxidiertem Si oder metallisiertem Si abgeschieden.The Carbon nanotubes are advantageously on a substrate of Si, oxidized Si or metallized Si deposited.
Die metallisierten Si-Substrate können mit Fe, Co oder Ni beschichtet sein.The metallized Si substrates can be coated with Fe, Co or Ni.
Gemäß einer Verfahrensvariante der Erfindung werden die Kohlenstoff-Nanoröhren im Abscheidungsreaktor ohne ein abscheidungsunterstützendes Substrat erzeugt und beschichtet.According to one Process variant of the invention, the carbon nanotubes in Deposition reactor produced without a deposition supporting substrate and coated.
Die erfindungsgemäß hergestellten ein- oder mehrwandigen, mit einem oder mehreren Übergangsmetallen beschichteten Kohlenstoff-Nanoröhren können in vielfältiger Weise vorteilhaft verwendet werden. Besonders vorteilhaft ist die Verwendung als nanostrukturierte Katalysatoren in industriellen chemischen Prozessen, die Verwendung als Katalysatoren für Methanol-Brennstoffzellen, die Verwendung als Kontaktwerkstoff in der Mikro- und Nanoelektronik und die Verwendung als Füllstoff in Kompositen mit einer Matrix aus Metall, Keramik oder Polymer.The produced according to the invention single- or multi-walled, coated with one or more transition metals Carbon nanotubes can in more diverse Be used advantageously way. Particularly advantageous is the Use as nanostructured catalysts in industrial chemical processes used as catalysts for methanol fuel cells, the use as a contact material in micro- and nanoelectronics and use as a filler in composites with a matrix of metal, ceramic or polymer.
Nachstehend ist die Erfindung an Hand von Ausführungsbeispielen näher erläutert.below The invention is explained in more detail with reference to exemplary embodiments.
Beispiel 1example 1
Das Beispiel betrifft die Herstellung von einwandigen, mit Palladium beschichteten Kohlenstoff-Nanoröhren.The Example relates to the production of single-walled palladium coated carbon nanotubes.
In einem vertikalen Quarzglasreaktor wird auf einem Substrathalter aus Stahl ein 10 × 10 mm oxidierter Siliziumwafer aufgebracht und zentrisch in Richtung der Gaseinströmung fixiert. Danach wird ein Argon-Gasstrom durch den Reaktor geleitet und der Bereich, in dem sich der Substrathalter befindet, durch eine induktive Heizung auf 820°C erwärmt.In a vertical quartz glass reactor is placed on a substrate holder made of steel a 10 × 10 mm oxidized silicon wafer applied and centric in the direction the gas inflow fixed. Thereafter, an argon gas stream is passed through the reactor and the area where the substrate holder is located an inductive heater at 820 ° C heated.
Eine präparierte Lösung von Ferrocen (19 mg/ml) und Pd(Acac)2 (40 mg/ml) in Azetonitril (approx 10 ml) in einem Ultraschallbad ausgesetzt. Die Ferrocen-Lösung dient als Precursor für die Synthese der Kohlenstoff-Nanoröhren. Die Pt-Lösung dient als Precursor für die Beschichtung der Kohlenstoff-Nanoröhren mit Pd.A prepared solution of ferrocene (19 mg / ml) and Pd (acac) 2 (40 mg / ml) in acetonitrile (approx 10 ml) was exposed in an ultrasonic bath. The ferrocene solution serves as a precursor for the synthesis of the carbon nanotubes. The Pt solution serves as a precursor for the coating of carbon nanotubes with Pd.
Nach dem Entstehen eines Aerosols über dem Lösungsgemisch wird das Aerosolgemisch mit einem Argon-Transportstrom in den Quarzglasreaktor eingebracht.To the formation of an aerosol the mixed solution the aerosol mixture is introduced into the quartz glass reactor with an argon transport stream brought in.
Nach einer Reaktionszeit von 30 Minuten bei Normaldruck wird der Ultraschall gestoppt. Nach weiteren 2 Minuten wird auch der Argonstrom durch die Lösung gestoppt und der Reaktor unter Argon abgekühlt.To a reaction time of 30 minutes at atmospheric pressure is the ultrasound stopped. After another 2 minutes, the argon flow is through the solution stopped and the reactor cooled under argon.
Im
Ergebnis dieser Verfahrensweise liegen, wie aus
Beispiel 2Example 2
Mit diesem Beispiel wird die Herstellung von einwandigen, mit Ru beschichteten Kohlenstoff-Nanoröhren beschrieben.With In this example, the production of single-walled, Ru-coated Carbon nanotubes described.
Verwendet wird hier ein horizontal angeordneter Quarzglasreaktor ohne Substrathalter und Wafer.used Here is a horizontally arranged quartz glass reactor without substrate holder and wafers.
Zunächst wird eine präparierte Lösung von Ferrocen (19 mg/ml) und Ru(Acac)3 (40 mg/ml) in Azetonitril (approx 10 ml) in einem Ultraschallbad ausgesetzt. Die Ferrocen-Lösung dient als Precursor für die Synthese der Kohlenstoff-Nanoröhren. Die Ru-Lösung dient als Precursor für die Beschichtung der Kohlenstoff-Nanoröhren mit Ru.First, a prepared solution of ferrocene (19 mg / ml) and Ru (Acac) 3 (40 mg / ml) in acetonitrile (approx. 10 ml) is exposed in an ultrasonic bath. The ferrocene solution serves as a precursor for the synthesis of the carbon nanotubes. The Ru solution serves as a precursor for the coating of carbon nanotubes with Ru.
Nach dem Entstehen eines Aerosols über dem Lösungsgemisch wird das Aerosolgemisch mit einem Argon-Transportstrom in den Quarzglasreaktor eingebracht, der eine etwa 20 cm lange induktiv auf etwa 830°C erwärmte Reaktionszone aufweist.To the formation of an aerosol the mixed solution the aerosol mixture is introduced into the quartz glass reactor with an argon transport stream introduced, the about 20 cm long inductively heated to about 830 ° C reaction zone having.
In
der Reaktionszone entsteht durch diese Verfahrensweise spontan ein
unorientierter Filz von Kohlenstoff-Nanoröhren.
Die
in der nachstehenden zur
- EDAX ZAF Quantification (Standardless)
- Element Normalized
- SEC Table: User c:\edax32\eds\genuser.sec
- c:\edax32\genesis\genspc.spc
- Label: ACW17_2
- Acquisition Time: 17:19:03; Date: 26-Jul-2006
- kU: 15.00 Tilt: 0.00; Take-off: 35.86; AmpT: 102.4
- Det Type: SUTW, Sapphire; Res: 129.65; Lsec: 100
- EDAX ZAF Quantification (Standardless)
- Element Normalized
- SEC Table: User c: \ edax32 \ eds \ genuser.sec
- c: \ edax32 \ genesis \ genspc.spc
- Label: ACW17_2
- Acquisition Time: 17:19:03; Date: 26-Jul-2006
- kU: 15.00 tilt: 0.00; Take-off: 35.86; AmpT: 102.4
- Det Type: SUTW, Sapphire; Res: 129.65; Lsec: 100
Literaturverzeichnisbibliography
- [1] M. S. Dresselhaus. G. Dresselhaus, Ph. Avouris (Eds.): CARBON NANOTUBES (Synthesis, structure, properties and applications) Springer Berlin, Heidelberg (Topics in Appl. Physics, Vol. 80)[1] M. S. Dresselhaus. G. Dresselhaus, Ph. Avouris (Eds.): CARBON NANOTUBES (Synthesis, structure, properties and applications) Springer Berlin, Heidelberg (Topics in Appl. Vol. 80)
-
[2]
DE 100 43 891 A1 DE 100 43 891 A1 - [3] B. M. Quinn, C. Dekker, S. G. Lemay: J. Am. Chem. Soc. 2005, 127, 6146-6147[3] B.M. Quinn, C. Dekker, S.G. Lemay: J. Am. Chem. Soc. 2005 127, 6146-6147
- [4] L. Qu, L. Dai: J. Am. Chem. Soc. 2005, 127, 10806-10807[4] L. Qu, L. Dai: J. Am. Chem. Soc. 2005, 127, 10806-10807
- [5] L. Qu, L. Dai, E. Osawa: J. Am. Chem. Soc. 2006, 128, 5523-5532[5] L. Qu, L. Dai, E. Osawa: J. Am. Chem. Soc. 2006, 128, 5523-5532
- [6] Y. Mu, H. Liang, J. Hu, L. Jiang, L. Wan: J. Phys. Chem. B 2005, 109, 22212-22216[6] Y. Mu, H. Liang, J. Hu, L. Jiang, L. Wan: J. Phys. Chem. B 2005, 109, 22212-22216
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