基于FeI2/Ni2+溶液还原制备低成本的高导电性及催化性纸张石墨

doi:10.15541/jim20170001

摘要/Abstract

摘要：

采用基于FeI₂/ Ni(NO₃)₂溶液的温和化学法还原制备低成本的纸张型石墨烯, 并对其导电与催化性能进行了研究。研究结果表明: 在pH=1.5, 温度为95℃的条件下处理6 h, 得到电导率高达30231 S/m的纸张型石墨烯, 这是由于作为强路易斯酸的Fe²⁺促进了亲核取代反应, 提高了还原效率, 从而提高了纸张型石墨烯的电导率; 而Ni²⁺通过减少溶液中的H⁺来抑制Fe²⁺的水解, 从而保证Fe²⁺对石墨烯的充分还原以及达到保护环境的目的。此外, 基于此还原工艺制备的纸张型石墨烯在I^-/I^3-电解液中可以获得接近铂电极的电流密度, 表明制备出的纸张型石墨烯具有较好的催化性能,并可以为电子提供快速的传出通道, 使其在太阳能电池中表现出较好的应用前景。

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关键词: 石墨烯, 金属离子, 化学还原, 电导率, 催化

Abstract:

A novel method to produce reductive graphene oxide (RGO) with FeI₂/Ni²⁺ applied as reductive agent was reported. This method provides a cheap, effective and environmentally friendly route for the large-scale production of RGO without losing its high conductivity and catalytic activity. An extremely high conductivity of 30231 S/m was obtained affer the optimized FeI₂/Ni(NO₃)₂ solution treatment. The enhancement of bulk conductivity was clue to the promotion of the nucleophilic substitution reaction induced by Fe²⁺(a strong Lewis acid). Ni²⁺was introduced to optimize the reductive process by reducing the concentration of hydrogen ions, which would inhibit the hydrolysis of Fe²⁺. Furthermore, a high cathodic peak current density was observed when applying the free-standing RGO paper as counter electrode in I^-/I^3- electrolyte system, indicating the high catalytic performance of the RGO paper and providing electron transporting pathway. These outstanding features exhibit a promising prospect of application in solar cells.

Key words: graphene oxide, metal iodides, chemical reduction, bulk conductivity, catalytic

中图分类号:

TQ174

南辉, 王文利, 韩建华, 尹学文, 周宇, 赵晓冲, 林红. 基于FeI₂/Ni²⁺溶液还原制备低成本的高导电性及催化性
纸张石墨[J]. 无机材料学报, 2017, 32(9): 997-1003.

NAN Hui, WANG Wen-Li, HAN Jian-Hua, YIN Xue-Wen, ZHOU Yu, ZHAO Xiao-Chong, LIN Hong. Low-cost Preparation of Graphene Papers from Chemical Reduction with FeI₂/Ni²⁺for Conductivity and Catalytic Propert[J]. Journal of Inorganic Materials, 2017, 32(9): 997-1003.

图/表 8

Fig. 1 Cross section SEM images of the original GO film (a) and RGO films (b) after reduction; Sheet resistance and conductivity of as-prepared RGO (c) reduced with different time (d), temperature (e), reductant (f)

Fig. 2 XRD patterns of raw graphite, GO, and RGO reduced with different reductant (a); by FeI2/Ni(NO3)2 with different temperatures (b) and for different time (c)

Fig. 3 FTIR spectra (a) and Raman spectra (b) of GO and RGO reduced by different reductan

Fig. 4 SEM images of GO (a, b) and TEM images of RGO (c, d) reduced with FeI2/Ni(NO3)2

Fig. 5 XPS spectra of GO (a) and those of corresponding RGO reduced with FeI2 (b) and FeI2/Ni(NO3)2 (c)

Table 1 ID/IG of GO and RGO reduced with different solutions

Sample	Reductant	I_D/(a.u.)	I_G/(a.u.)	I_D/I_G
GO		499.7	462.5	1.08
RGO	FeI₂	377.3	237.3	1.59
RGO	FeI₂/NiCl₂	402.2	251.7	1.60
RGO	FeI₂/Ni(NO₃)₂	389.6	250.2	1.66
RGO	FeI₂/NiSO₄	564.8	389.2	1.45

Fig. 6 Changes of color of different reductant with time (a) FeI2; (b) FeI2/Ni(NO3)2

Fig. 7 CV curves for RGO reduced with different reductant (a) and CV curves for RGO reduced by FeI2/ Ni(NO3)2 with different cycle numbers (b)

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基于FeI₂/Ni²⁺溶液还原制备低成本的高导电性及催化性
纸张石墨

Low-cost Preparation of Graphene Papers from Chemical Reduction with FeI₂/Ni²⁺for Conductivity and Catalytic Propert

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