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首頁» 過刊瀏覽» 2020» Vol.5» Issue(4) 578-586???? DOI : 10.3969/j.issn.2096-1693.2020.04.051
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中間相瀝青基摻氮碳量子點的制備及其熒光特性
寧國慶 ,,王海斌,,楊帆,,李永峰
中國石油大學(北京)重質(zhì)油國家重點實驗室,,北京 102249
Synthesis of mesophase pitch-based N-doped carbon quantum dots and their fluorescence properties
NING Guoqing, WANG Haibin, YANG Fan, LI Yongfeng
State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, China

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摘要? 由中間相瀝青中的納米尺度碳質(zhì)微晶,,直接碳化制備碳量子點(CQDs),是制備碳量子點的新方法,。本文 在此方法的基礎(chǔ)上,對中間相瀝青基碳量子點的摻氮工藝及其熒光特性進行了系統(tǒng)考察,。采用兩種方法制備摻 氮碳量子點 (NCQDs),,一種是用氮等離子體轟擊中間相瀝青基CQDs,另一種方法是在原料油中混入三聚氰胺,, 制備摻氮中間相瀝青,,進而將摻氮的碳質(zhì)微晶分散在硅片上,碳化得到NCQDs,。對所得NCQDs,,我們采用掃描 電子顯微鏡、透射電子顯微鏡和原子力顯微鏡進行表征,,并進行了X射線光電子譜和熒光發(fā)射光譜分析。氮等 離子體轟擊制備的NCQDs (NCQDs-P)中,,氮元素主要以吡啶氮和石墨氮的形式存在,,等離子體轟擊并未明顯改 變碳量子點的尺寸。而三聚氰胺法制備的NCQDs(NCQDs-C)中氮元素主要為吡咯氮和石墨氮,,隨著三聚氰胺添 加量的增加,,NCQDs-C的粒徑由 2.2 nm增長至 4.5 nm。這可能是由于含氮基團具有較高反應(yīng)活性,,加快了瀝青 大分子的聚合過程,,使得在相同煅燒溫度和時間下得到了更大尺寸的碳質(zhì)微晶。NCQDs-C與未摻雜N的CQDs 的熒光特性相似,,熒光峰位置不隨激發(fā)波長變化而變化,。與之不同,,NCQDs-P熒光峰位置隨激發(fā)波長位置移動 而變化,且等離子體轟擊時間越長,,NCQDs-P熒光峰位置移動越明顯,,這是因為吡啶氮的引入增加了碳材料在 費米能級附近的態(tài)密度,導致激發(fā)態(tài)能隙減小,,內(nèi)轉(zhuǎn)化和振動弛豫變得容易,。本研究表明,兩種摻氮方法均可 以實現(xiàn)氮摻雜碳量子點的高效制備,,獲得的摻雜碳量子點具有均一的粒徑分布,,N/C原子比可達 8.3%,但是兩 種摻氮方法對碳量子點的尺寸和摻氮的類型會產(chǎn)生不同的影響,,并進一步影響到摻氮碳量子點的熒光特性,。
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關(guān)鍵詞 : 中間相瀝青,;碳量子點;摻氮
Abstract
Direct carbonization of dispersed carbonaceous microcrystals in mesophase pitch is a new approach to the synthesis of carbon quantum dots (CQDs). Based on this new method, this work presents a systematic investigation of the synthesis and fluorescence characterization of N-doped CQDs (NCQDs) derived from mesophase pitch. Two different methods are adopted to produce NCQDs: 1) Nitrogen plasma bombardment of the CQDs prepared from mesophase pitch, and 2) Carbonization of  N-doped carbonaceous microcrystals, which are prepared by introducing melamine into raw oil. In the nitrogen plasma bom-   bardment synthesis, a nitrogen plasma was produced at 220   -   230 V bias voltage with a discharge current of 0.128 A. The plasma    treatment time was 5, 20 and 30 min. In the synthesis using melamine, the oil slurry to melamine mass ratios of 4:1 and 1:1 were    tested. The as-prepared NCQDs were characterized by scanning and transmission electron microscopy, atomic force microscopy,    X-ray photoelectron spectroscopy and photoluminescence emission spectroscopy. Our results show that both methods are capable    of producing NCQDs, with an N to C molar ratio of up to 8.3   %   . On the other hand, the two different synthesis methods affect    the particle size and the N atom configuration of NCQDs, consequently resulting in different fluorescence characteristics. In the    NCQDs prepared with plasma (NCQDs-P), N atoms are mainly in the configurations of pyridinic and graphitic N, while the N    binding modes of NCQDs prepared with melamine (NCQDs-C) are pyrrolic and graphitic N. The nitrogen plasma bombardment    has not significantly changed the particle size of CQDs. However, the particle size of NCQDs-C increases from 2.2 nm to 4.5 nm    as the added amount of melamine increases. It is likely due to the higher reactivity of N-doped groups, which might have accel   erated the aggregation of pitch molecules and resulted in larger carbonaceous microcrystals at the same calcination temperature    and time. In the fluorescence curves of NCQDs-C and the undoped CQDs, the fluorescence peak positions do not change with    the excitation wavelength, while the peaks for NCQDs-P change as the excitation wavelength varies. Larger peak movement in    the fluorescence curve for NCQDs-P is observed at longer plasma etching time. It is likely due to the introduction of pyridinic N,    which has increased state density near the Fermi level and consequently reduced the energy gap between different excited states,    thus leading to easier internal conversion and vibration relaxation. Our work provides a new approach to efficient synthesis of    NCQDs, and gives a better understanding of the effect of N atom configuration on the fluorescence properties of CQDs.  


Key words: mesophase pitch, carbon quantum dots; nitrogen doping
收稿日期: 2020-12-30 ????
PACS: ? ?
基金資助:由國家自然科學基金面上項目( 批準號 21776309) 資助
通訊作者: [email protected]
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NING Guoqing, WANG Haibin, YANG Fan, LI Yongfeng. Synthesis of mesophase pitch-based N-doped carbon quantum dots and their fluorescence properties. Petroleum Science Bulletin, 2020, 04: 578-586.
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