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Chimie

Oda sıcaklığında karbon Nanosheets hazırlanması

Published: March 08, 2016
doi:
10.3791/53505
, , , , ,
1Institute of Materials,Ecole Polytechnique Fédérale de Lausanne (EPFL), 2Colloid Chemistry Department,Max Planck Institute of Colloids and Interfaces

Summary

We present the synthesis of an amphiphilic hexayne and its use in the preparation of carbon nanosheets at the air-water interface from a self-assembled monolayer of these reactive, carbon-rich molecular precursors.

Abstract

Amphiphilic molecules equipped with a reactive, carbon-rich “oligoyne” segment consisting of conjugated carbon-carbon triple bonds self-assemble into defined aggregates in aqueous media and at the air-water interface. In the aggregated state, the oligoynes can then be carbonized under mild conditions while preserving the morphology and the embedded chemical functionalization. This novel approach provides direct access to functionalized carbon nanomaterials. In this article, we present a synthetic approach that allows us to prepare hexayne carboxylate amphiphiles as carbon-rich siblings of typical fatty acid esters through a series of repeated bromination and Negishi-type cross-coupling reactions. The obtained compounds are designed to self-assemble into monolayers at the air-water interface, and we show how this can be achieved in a Langmuir trough. Thus, compression of the molecules at the air-water interface triggers the film formation and leads to a densely packed layer of the molecules. The complete carbonization of the films at the air-water interface is then accomplished by cross-linking of the hexayne layer at room temperature, using UV irradiation as a mild external stimulus. The changes in the layer during this process can be monitored with the help of infrared reflection-absorption spectroscopy and Brewster angle microscopy. Moreover, a transfer of the carbonized films onto solid substrates by the Langmuir-Blodgett technique has enabled us to prove that they were carbon nanosheets with lateral dimensions on the order of centimeters.

Introduction

İki boyutlu karbon nano yapılar nedeniyle rapor üstün termal, elektrik, hem de mekanik özellikleri 1-5 önemli dikkat çekmek. Bu malzemeler Polimer kompozit 6, enerji depolama aygıtları 7 ve moleküler elektronik 8-10 alanlarında teknik ilerlemesinin bekleniyor. Son yıllarda yoğun araştırma çabalarına rağmen, iyi tanımlanmış karbon nano malzemelerin büyük miktarlarda erişim hala teknolojik uygulamalar 11,12 onların büyük ölçekli uygulama engellemektedir hangi sınırlıdır.

Karbon nanomalzemeleri ya yukarıdan aşağı ya da aşağıdan yukarıya yaklaşımlarla erişilebilir. Bu tür yüzeylerde 14-16 pul pul dökülme teknikleri 13 veya yüksek enerjili süreçleri gibi tipik yaklaşımlar yapısal mükemmellik ve çok iyi bir performans yüksek derecede malzeme elde etmek imkanı sunuyoruz. Bununla birlikte, yalıtım ve inci saflaştırılmasıe ürünler zorlu kalır ve tanımlı Nanoyapılı malzemelerin büyük ölçekli üretim zor 12'dir. Öte yandan, aşağıdan yukarıya yaklaşımlar, molekül öncüleri kullanımına dayalı bu tanımlı yapılara düzenleme ve karbon nano 17-23 veren bir sonraki karbonizasyon kullanılabilir. Bu durumda, ön-kendilerini daha karmaşıktır ve bunların hazırlanması, genellikle birden fazla sentetik adım gerektirir. Bu yaklaşımlar ortaya çıkan malzemelerin kimyasal ve fiziksel özellikleri üzerinde kontrol yüksek derecede sunabilir ve özel malzemelere doğrudan erişim vermek olabilir. Bununla birlikte, C-nano içine öncüler dönüştürülmesi, genellikle gömülü kimyasal işlevsellik 24-27 bir kaybına yol açar, 800 ° C'nin üzerindeki sıcaklıklarda gerçekleştirilir.

Yukarıda belirtilen sınırlamalar bu ca yüksek reaktif oligoynes kullanılarak grubumuza ele alınmıştırN, oda sıcaklığında 28,29 karbon nano haline dönüştürülebilir. Özel olarak, bir hidrofilik baş grubu ve bir hexayne segmenti içeren amfifiller brominasyon ve paladyum dolayımlı Negishi çapraz birleştirme reaksiyonları 30,31 bir dizi erişilebilir. Hedef yapı halinde, bu haberci moleküllerin dönüşüm ya da UV ışığı ile ışınlama sırasında oda sıcaklığının altında meydana gelir. oligoyne amfifillerin yüksek reaktivitesi, muhtemel hava-su ara ya da sıvı-sıvı arayüzlerine yumuşak şablonlar, kullanır. Önceki araştırmalarda, başarıyla hexayne glikozit amfifillerin 28 çözümlerinden veziküller hazırlanmıştır. Bu veziküller çapraz bağlanması numunelerin UV ışınımı ile yumuşak koşullar altında elde edilmiştir. Ayrıca, kısa bir süre önce bir metil karboksilat baş grubu ve bir Langmuir teknedeki hava-su ara yüzeyinde bir hidrofobik alkil kuyruk hexaynes kendi kendine monte mono tabakaları elde. yoğun paketed molekül ön sonra düpedüz UV ışıması ile, oda sıcaklığında kendinden destekli C nanosheets dönüştürüldü. İlgili yaklaşımlarda tarif molekül ön en son hava-su arayüzünde 32-38 iki boyutlu genişletilmiş nanosheets hazırlanması için kullanılmıştır.

Bu çalışmanın amacı, hexayne amfifillerin karbon nanosheets hazırlanmasına olanak genel sentez ve üretim aşamalarının bir özlü, pratik bir bakış vermektir. Odak deneysel yaklaşım ve hazırlayıcı sorular yer almaktadır.

Protocol

Dikkat: Herhangi bir kimyasal bileşiklerin kullanılmadan önce ilgili malzemeler güvenlik bilgi formlarını (MSDS) bakın emin olun. ve bu sentezlerde kullanılan kimyasalların bazıları, akut olarak toksik ve kanserojen. Hazırlanan nanomalzemeler kendi toplu meslektaşı ile karşılaştırıldığında ek tehlikeler olabilir. Reaksiyonlar (davlumbaz) ve kişisel koruyucu donanımlar (koruyucu gözlük, eldiven, laboratuvar önlüğü, tam uzunlukta pantolon, kapalı-toe ayakkabıları) yaparken tüm uygun güve…

Representative Results

Hazırlanan prekürsör molekülünün 13C nükleer manyetik rezonans (NMR) spektrumu 3 görüntüler δ = 82-60 ppm (Şekil 1b) karşılık gelen bir kimyasal kaymalarla hexayne segmentinin 12 sp -hybridized C-atomu içerir. Ayrıca, δ = 173 ppm ve δ = 52 ppm'de sinyaller, sırasıyla, esterin karbonil ve metil karbon atanır. δ = 33-14 ppm arasında sinyal dodesil kalıntısının alifatik karbon atfedilmektedir. 3</s…

Discussion

İstenen hexayne amfifil (3) düpedüz sıralı brominasyon 52,53 hazırlanır ve tritylphenyl ester (2) (Şekil 1a) 29 bir son koruma giderme reaksiyonu ile, alkin segmentin uzama 30,31 Pd-katalizli izledi. Başarılı sentezi 31,54 13C NMR tayfı (Şekil 1B) hem de UV-Vis emilme tayfı (Şekil 1c) teyit edilir. Bu, daha yüksek oligoyne homologlarını geliştirilen sentetik yöntem 30,31 hazırlanabili…

Divulgations

The authors have nothing to disclose.

Acknowledgements

Funding from the European Research Council (ERC Grant 239831) and a Humboldt Fellowship (BS) is gratefully acknowledged.

Materials

Methyllithium lithium bromide complex (2.2M solution in diethylether) Acros 18129-1000 air-sensitive, flammable
Zinc chloride (0.7M solution in THF) Acros 38945-1000 air-sensitive, flammable
1,1'-Bis(diphenylphosphino)ferrocene]
dichloropalladium(II), DCM adduct 		 Boron Molecular BM187
N-Bromosuccinimide Acros 10745 light-sensitive
Silver fluoride Fluorochem 002862-10g light-sensitive
n-Butyllithium (2.5M solution in hexanes) Acros 21335-1000 air-sensitive, flammable
Sodium methanolate Acros 17312-0050
Tetrahydrofuran (unstabilized, for HPLC) Fisher Chemicals T/0706/PB17 This solvent was dried as well as degassed using a solvent purification system (Innovative Technology, Inc, Amesbury, MA, USA)
Toluene (for HPLC) Fisher Chemicals T/2306/17 This solvent was dried as well as degassed using a solvent purification system (Innovative Technology, Inc, Amesbury, MA, USA)
Acetonitrile (for HPLC) Fisher Chemicals A/0627/17 This solvent was dried as well as degassed using a solvent purification system (Innovative Technology, Inc, Amesbury, MA, USA)
Dichloromethane (Extra Dry over Molecular Sieve) Acros 34846-0010
Chloroforme (p.a.) VWR International 1.02445.1000
Pentane Reactolab 99050 Purchased as reagent grade and distilled once prior to use
Heptane Reactolab 99733 Purchased as reagent grade and distilled once prior to use
Dichloromethane Reactolab 99375 Purchased as reagent grade and distilled once prior to use
Diethylether Reactolab 99362 Purchased as reagent grade and distilled once prior to use
Geduran silica gel (Si 60, 40-60µm) Merck 1115671000
Langmuir trough R&K, Potsdam
Thermostat  E1 Medingen
Hamilton syringe  Model 1810 RN SYR
Vertex 70 FT-IR spectrometer  Bruker
External air/water reflection unit (XA-511)  Bruker
UV lamp (250 W, Ga-doped metal halide bulb) UV-Light Technology
Brewster angle microscope (BAM1+)  NFT Göttingen
Sapphire substrates Stecher Ceramics
Quantifoil holey carbon TEM grids Electron Microscopy Sciences
Nuclear magnetic resonance spectrometer (Bruker Avance III 400) Bruker
JASCO V-670 UV/Vis spectrometer JASCO
Scanning Electron Microscope (Zeiss Merlin FE-SEM) Zeiss
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Tags

Carbon NanosheetsRoom TemperatureWet Chemical PreparationSelf-assemblyAmphiphilic MoleculesCarbonizationUV IrradiationHexayneLangmuir TroughInfrared Reflection Absorption Spectroscopy
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Schrettl, S., Schulte, B., Stefaniu, C., Oliveira, J., Brezesinski, G., Frauenrath, H. Preparation of Carbon Nanosheets at Room Temperature. J. Vis. Exp. (109), e53505, doi:10.3791/53505 (2016).
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