本文選題：苯二胺 + 炭黑�。� 參考：《催化學(xué)報》2016年07期

【摘要】：近年來,氮摻雜的碳材料作為堿性氧還原催化劑得到了研究者的廣泛關(guān)注.摻雜的N原子會影響C原子的自旋密度和電荷分布,導(dǎo)致碳材料表面產(chǎn)生"活性位點",因此摻氮碳材料具有優(yōu)秀的氧還原活性,這已經(jīng)在理論計算和實驗中得到了驗證.我們通過調(diào)節(jié)聚對苯二胺和碳黑的比例,之后進行熱解制備了一系列摻氮碳材料.其中0.88PpPD/CB樣品具有最好的氧還原活性,其在KOH溶液(0.1 mol/L)中的氧還原性能超過了商業(yè)碳載鉑.通過掃描電子顯微鏡表征,發(fā)現(xiàn)碳球聚集在聚對苯二胺的表面,這主要是因為聚對苯二胺沒有進行酸摻雜,因此其水溶性比較差.通過氮氣的吸脫附表征,發(fā)現(xiàn)聚對苯二胺的比表面積很小,而碳黑樣品(BP2000)的比表面積很大.因此,隨著聚對苯二胺量的增加,聚對苯二胺/碳黑復(fù)合物的比表面積逐漸降低.另外,聚對苯二胺表面幾乎都是微孔,而介孔和大孔主要來自于碳黑.研究者認(rèn)為,"活性位點"主要位于微孔內(nèi)(聚對苯二胺表面),而介孔和大孔有利于物質(zhì)的傳輸.因此,當(dāng)聚對苯二胺和碳黑的比例合適時,既有大量的"活性位點"暴露,又有足夠的介孔和大孔進行物質(zhì)傳輸,所以0.88PpPD/CB樣品的氧還原活性最高.但是,對于摻氮碳材料來說,一個主要的問題就是穩(wěn)定性不足.不管是電化學(xué)穩(wěn)定性,還是放置在空氣中的穩(wěn)定性,摻氮碳材料都比不上鉑基催化劑,這也阻礙了它們的大規(guī)模應(yīng)用.對于電化學(xué)穩(wěn)定性,很多文章都進行了報道,但是很少有文章報道摻氮碳材料在空氣中的穩(wěn)定性.我們知道,鉑基材料之所以具有優(yōu)異的氧還原活性,是因為鉑和氧氣的結(jié)合能比較合適,既利于氧氣吸附,也利于之后氧氣分子鍵的斷裂.但是,當(dāng)鉑基材料放置在空氣中,氧氣的吸附也會發(fā)生,而且之后會導(dǎo)致表面氧化層的形成.所以鉑基材料需要活化才能達到最好的催化性能.對于摻氮碳材料,放置在空氣中會不會發(fā)生氧化反應(yīng)?這對氧還原活性是否有影響?為了研究摻氮碳材料在空氣中的穩(wěn)定性,我們將0.88PpPD/CB樣品在空氣中放置了一個月,之后再進行電化學(xué)測試.旋轉(zhuǎn)圓盤電極測試表明,在空氣中放置了一個月后,0.88PpPD/CB樣品的氧還原活性降低了,不管是半波電位還是極限電流密度都下降了.之后我們對其進行了X射線光電子能譜檢測,發(fā)現(xiàn)在空氣中放置了一個月后其氧含量提高了1%(原子分?jǐn)?shù)),而氮含量幾乎沒有變化.氧含量的提高證實了氧化反應(yīng)的發(fā)生,但不能直接歸結(jié)于空氣中的氧氣.為了排除其他因素,如水蒸氣、二氧化碳等,當(dāng)熱處理完成,管式爐溫度低于100°C時,我們將高純氮氣切換為高純氧氣,一個小時后再取出樣品.電化學(xué)測試表明,在氧氣中暴露了一個小時后,0.88PpPD/CB樣品的氧還原活性極大地降低了,而且X射線光電子能譜表明其氧含量提高了一倍,接近12%.因此,我們證實了氧氣會和0.88PpPD/CB樣品反應(yīng),導(dǎo)致樣品的氧還原活性降低.所以,對于未來摻氮碳材料的大規(guī)模應(yīng)用,要考慮其在空氣中的穩(wěn)定性,以及如何避免和氧氣接觸.
[Abstract]:In recent years, nitrogen doped carbon materials have been widely concerned as basic oxygen reduction catalysts. Doping N atoms will affect the spin density and charge distribution of C atoms, resulting in the production of "active sites" on the surface of carbon materials. Therefore, nitrogen doped carbon materials have excellent oxygen reduction activity, which has been obtained in theoretical calculation and experiment. By adjusting the ratio of polyphenylene two and carbon black, we prepared a series of nitrogen doped carbon materials by pyrolysis, in which the 0.88PpPD/CB samples had the best oxygen reduction activity and the oxygen reduction performance in the KOH solution (0.1 mol/L) exceeded the commercial carbon loaded platinum. The surface of benzyl two amine is mainly due to the poor water solubility of polyphenylene two amine, so its water solubility is poor. It is found that the specific surface area of polyphenylene two amine is very small and the specific surface area of carbon black sample (BP2000) is very large. Therefore, the ratio of polyphenylene two amines increases with the increase of polyphenylene two amine / carbon black complex. The surface area is gradually reduced. In addition, the surface of polyphenylene two amine is almost all micropores, and mesoporous and large pores mainly come from carbon black. The researchers believe that the "active site" is mainly located in the micropores (polyphenylene two amines surface), while mesoporous and pore are beneficial to the transfer of material. Therefore, when the proportion of polyphenylene two amines and carbon black is suitable, there is a large amount of "live". 0.88PpPD/CB samples have the highest oxygen reduction activity. However, for nitrogen doped carbon materials, one of the main problems is the lack of stability. No matter the electrochemical stability or the stability in the air, the nitrogen doped carbon materials are not more than the platinum based catalysts. Many articles have been reported on electrochemical stability, but few articles report on the stability of nitrogen doped carbon materials in the air. We know that the excellent oxygen reduction activity of platinum based materials is because the combination of platinum and oxygen is more suitable and is beneficial to oxygen adsorption. It also helps to break the oxygen molecular bond. But when the platinum material is placed in the air, the adsorption of oxygen will also occur, and then the formation of the surface oxide layer. Therefore, the platinum base material needs activation to achieve the best catalytic performance. Is there an effect on the original activity? In order to study the stability of nitrogen doped carbon materials in the air, we put 0.88PpPD/CB samples in the air for one month and then carry out electrochemical tests. The rotating disk electrode test showed that after one month in the air, the oxygen reduction activity of 0.88PpPD/CB samples decreased, no matter the half wave potential. The limit current density decreased. Then we tested it by X ray photoelectron spectroscopy, and found that after a month in the air, the oxygen content increased by 1% (atomic fraction), and the nitrogen content was almost unchanged. In addition to other factors, such as water vapor, carbon dioxide, and so on, when the heat treatment is completed and the tube furnace temperature is below 100 C, we switch high pure nitrogen to high pure oxygen, and then take out the sample after one hour. The electrochemical test shows that after an hour of exposure to oxygen, the oxygen reduction activity of the 0.88PpPD/CB sample is greatly reduced, and the X ray light is greatly reduced. The electron spectrum showed that the oxygen content increased by one time. As close to 12%., we confirmed that oxygen would react with the 0.88PpPD/CB sample and reduce the oxygen reduction activity of the sample. Therefore, for the large-scale application of nitrogen doped carbon materials in the future, the stability in the air and how to avoid contact with oxygen should be considered.

【作者單位】： 南京大學(xué)現(xiàn)代工程與應(yīng)用科學(xué)學(xué)院;南京大學(xué)固體微結(jié)構(gòu)物理國家重點實驗室人工微結(jié)構(gòu)科學(xué)與技術(shù)協(xié)同創(chuàng)新中心;南京大學(xué)昆山創(chuàng)新研究院;南京大學(xué)(蘇州)高新技術(shù)研究院;
【基金】：supported by the National Natural Science Foundation of China(21476104) the Natural Science Foundation for Distinguished Young Scholars of Jiangsu Province(BK20150009) the Natural Science Foundation for Young Scholars of Jiangsu Province(BK20150396) the Soft Science Research Program of Jiangsu Province(BR2015009) the Nanotechnology Program of Suzhou(ZXG2013029) the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions,Qing Lan Project of Jiangsu Province the Fundamental Research Funds for the Central Universities,China~~
【分類號】：O643.36

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