Department of Fibre and Polymer Technology, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Stockholm, Sweden.
Nanoscale. 2017 Jul 13;9(27):9562-9571. doi: 10.1039/c7nr02943h.
The electrical conductivity of reduced graphene oxide (rGO) obtained from graphene oxide (GO) using sodium borohydride (NaBH) as a reducing agent has been investigated as a function of time (2 min to 24 h) and temperature (20 °C to 80 °C). Using a 300 mM aqueous NaBH solution at 80 °C, reduction of GO occurred to a large extent during the first 10 min, which yielded a conductivity increase of 5 orders of magnitude to 10 S m. During the residual 1400 min of reaction, the reduction rate decreased significantly, eventually resulting in a rGO conductivity of 1500 S m. High resolution XPS measurements showed that C/O increased from 2.2 for the GO to 6.9 for the rGO at the longest reaction times, due to the elimination of oxygen. The steep increase in conductivity recorded during the first 8-12 min of reaction was mainly due to the reduction of C-O (e.g., hydroxyl and epoxy) groups, suggesting the preferential attack of the reducing agent on C-O rather than C[double bond, length as m-dash]O groups. In addition, the specular variation of the percentage content of C-O bond functionalities with the sum of Csp and Csp indicated that the reduction of epoxy or hydroxyl groups had a greater impact on the restoration of the conductive nature of the graphite structure in rGO. These findings were reflected in the dramatic change in the structural stability of the rGO nanofoams produced by freeze-drying. The reduction protocol in this study allowed to achieve the highest conductivity values reported so far for the aqueous reduction of graphene oxide mediated by sodium borohydride. The 4-probe sheet resistivity approach used to measure the electrical conductivity is also, for the first time, presented in detail for filtrate sheet assemblies' of stacked GO/rGO sheets.
采用硼氢化钠(NaBH)作为还原剂,将氧化石墨烯(GO)还原得到的还原氧化石墨烯(rGO)的电导率随时间(2 分钟至 24 小时)和温度(20°C 至 80°C)的变化关系进行了研究。在 80°C 下,使用 300mM 的 NaBH 水溶液,GO 在最初的 10 分钟内发生了很大程度的还原,电导率提高了 5 个数量级,达到 10 S m。在剩余的 1400 分钟反应时间内,还原速率显著下降,最终得到 rGO 的电导率为 1500 S m。高分辨率 XPS 测量表明,C/O 比从 GO 的 2.2 增加到 rGO 的 6.9,这是由于氧的消除。在反应的最初 8-12 分钟内记录到的电导率急剧增加主要归因于 C-O(例如,羟基和环氧)基团的还原,这表明还原剂优先攻击 C-O 而不是 C[双键,长度为 m-dash]O 基团。此外,C-O 键官能团的百分比含量与 Csp 和 Csp 的总和的镜面变化表明,环氧或羟基基团的还原对 rGO 中石墨结构导电性质的恢复有更大的影响。这些发现反映在由冷冻干燥制备的 rGO 纳米泡沫结构稳定性的显著变化上。本研究中的还原方案使得通过硼氢化钠介导的氧化石墨烯水还原能够实现迄今为止报道的最高电导率值。用于测量电导率的四点探针片电阻率方法也首次详细介绍了用于堆叠 GO/rGO 片的过滤片组件。