氧化石墨烯和還原氧化石墨烯的應用

Avery Luedtke, Ph.D.

MilliporeSigma, Milwaukee, WI

簡介

氧化石墨烯（GO，產品編號 763705 and 777676）是一種獨特的材料，可視為具有各種含氧官能性（如環氧基、羰基、羧基和羥基）的單分子石墨層。^1,2,3 在石墨烯（單層石墨）首次被分離和研究之後，人們對 GO 的興趣急劇增加。⁴ 最初人們希望 GO 可以成為石墨烯的合成前體。⁵ 當具有電絕緣性的 GO 被還原時， 還原氧化石墨烯 ；(GO, product number 777684)所形成的氧化石墨烯類似石墨烯，但含有殘留的氧和其他雜原子以及結構缺陷。^6,7 如何製造出更接近原始石墨烯的 rGO，是這個領域的一大挑戰。儘管如此，由於 rGO 可以從 GO 在水中的水性分散液製成薄膜，且具有中等的導電性，因此在電子裝置中的應用相當具有吸引力。^8,9,10,11,12 除了作為電子設備的元件之外，GO 和 rGO 還被用於納米複合材料、^13,14 聚合物複合材料、¹³ 能量儲存、^{14能量儲存、14 生物醫學應用、15,16,17 催化、18,19,20 以及作為表面活劑21 這些領域之間有一些重疊。} 

GO的合成和還原

合成GO的許多現代程序都是基於Hummers首先報告的方法，其中石墨被硫酸中的高錳酸鉀溶液氧化。²² 也有使用肼還原 GO 的報導。⁵ 然而，肼具有很高的毒性，而且有可能使 GO 功能化為氮雜質原子。²³ 由於這些問題，肼的替代品包括 NaBH₄、¹⁴²⁴ 和 HI^25、26 等已被用於還原 GO。GO 可以以薄膜或水溶液的形式還原。⁶

電子

有幾種電子裝置是使用 GO 作為至少一種元件的起始材料製造出來的。^27,28 採用 rGO 的場效應電晶體 (FET) 已被用作化學感測器^29,30,31 和生物感測器。³¹ 使用功能化 rGO 作為半導體的 GFET 已被用作生物傳感器來檢測荷爾蒙兒茶酚胺分子、³² 阿維丁、³³ 和 DNA。³⁴ In another study, GO that was functionalized with glucose oxidase and deposited on an electrode was used as an electrochemical glucose sensor.³⁵

Visible light transparent electrodes are important for both light emitting diodes (LEDs) and solar cell devices.由於 GO 可以在溶液中進行加工，因此使用 rGO 作為透明電極，對於這些裝置而言，是其他透明電極 (例如 ITO) 的方便替代品。^36,37 除了作為透明電極之外，rGO 還被用作聚合物太陽能電池和發光二極管^38,39

中的空穴傳輸層。

圖 1. (a) 在 Si/SiO2 基板上用作氣體感測器的典型後閘極 GFET。(b) 軟性聚對苯二甲酸乙二醇酯 (PET) 基板上的典型溶液閘極 GFET，用於水溶液中的化學和生物傳感器。經國家科學研究中心 (CNRS) 及英國皇家化學會許可，轉載自參考文獻 31。

能源儲存

rGO 的奈米複合材料已被用於鋰離子電池的高容量能源儲存。在這些研究中，電絕緣的金屬氧化物奈米粒子被吸附在 rGO 上，以增加這些材料在電池中的效能。^{40,41,42,43,44} 例如，Fe₃O₄ 的能量儲存容量和週期穩定性都有增加。/或 Fe₂O₃  (圖 2)。⁴³ 利用微波進行 GO 的剝離和還原，製造出高表面面積的 rGO。所形成的高比表面積 rGO 可作為超級電容中的能量儲存材料。

圖 2. (a) GNS/Fe3O4 複合物的放電/充電剖面。(b) 商用 Fe3O4 顆粒、GNS/Fe3O4 複合物和裸 Fe2O3 顆粒在電流密度為 35 mA/g 時的循環效能 實心符號表示放電；空心符號表示充電。(c) GNS/Fe3O4 複合物在 700 mA/g 電流密度下 100 次循環時的循環效能。(d) 商用 Fe3O4 顆粒、GNS/Fe3O4 複合物和裸 Fe2O3 顆粒在不同電流密度下的速率效能。GNS = rGO。經參考 43 許可改編。版權所有 2010 美國化學學會。

生物醫學應用

GO在生物醫學領域的一個用途是作為藥物傳輸系統的成分。 Functionalized nanographene oxide (nGO, product number 795534)已被用於多項抗癌藥物靶向傳遞的研究中。聚乙二醇 (PEG) 功能化的 nGO 含有 SN38，一種 喜樹堿 （產品編號 H0165）的衍生物，吸附在表面上（nGO-PEG-SN38）被用來作為藥物的水溶性和血清溶解性來源。⁴⁷ 在該研究中，nGO-PEG-SN38在降低人類結腸癌細胞株HTC-116的細胞活力方面，比FDA批准的SN38原藥伊立替康（CPT-11）有效三個數量級（圖3）。⁴⁷ nGO-PEG-SN38的有效性與DMSO中的SN38相似（圖3）。⁴⁷ 小鼠的黑色素瘤皮膚癌已經用近紅外線雷射和nGO的光熱消融療法治療，nGO是用PEG和透明質酸功能化，並經皮下傳遞。⁴⁸ 在另一項研究中，磁鐵被吸附在載有抗癌藥物鹽酸多柔比星（DXR，產品編號 44583），利用磁鐵將藥物靶向傳遞到特定部位。⁴⁹

。

圖 3. 體外細胞毒性試驗。(a) HCT-116 細胞與不同濃度的 CPT-11、SN38 及 NGO-PEG-SN38 培養 72 小時後的相對細胞存活率 (相對於未處理的對照) 數據。水溶性 NGO-PEG-SN38 在 DMSO 中顯示出與 SN38 相似的毒性，且效力遠高於 CPT-11。(b) HCT-116 細胞與含有 (紅色) 和不含 (黑色) SN38 的 nGO-PEG 培養後的相對細胞存活率資料。即使在非常高的濃度下，普通的 NGO-PEG 也沒有明顯的毒性。誤差條基於三重樣本。NGO = nGO。經參考 47 許可改編。版權所有 2008 美國化學會。

生物感測器

GO和rGO已被用作幾個系統的元件，這些系統旨在檢測生物相關分子。在利用螢光共振能量轉移 (FRET) 效應的生物感測器中，GO 已經被用作螢光淬滅材料。在 Lu 等人的一項研究中，帶有螢光標籤的單鏈 DNA (ssDNA) 被發現與 GO 非共价地結合，隨後標籤的螢光會被淬滅。⁵⁰ 加入互補的 ssDNA 可將標籤 DNA 從 GO 表面移除，並恢復螢光。⁵¹ Folic acid functionalized GO was used as a component in a system used to detect human cervical cancer and human breast cancer cells.⁵²

我們提供高品質的氧化石墨烯產品，滿足您的創新和先進材料研究需求。如需可用的石墨烯和氧化石墨烯產品清單，請造訪 sigmaaldrich.com/nanocarbons.

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材料

抱歉，發生意外錯誤。

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