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The diamond/graphene composite electrode has garnered significant attention due to its ability to synergistically combine the low background current and broad potential window of the diamond component with the high electrochemical activity of the graphitic component. In this study, argon-oxygen plasma etching is employed to treat nanodiamond/graphite composite films, and the surface structure of the few-layer graphene-coated nanodiamond is obtained by adjusting the etching time to control the number of graphite layers on the surface of the film, and then the surface layer of the few-layer graphene-coated nanodiamond and the bottom layer with good conductivity with more graphite components are constructed to form a double-layer structure. The experimental findings demonstrate that when the argon/oxygen plasma treatment time reaches 5 min, the graphite components on the surface layer of the film are etched into a structure of small-layer graphite coated nanodiamond, which increases the resistivity (2918.3 Ω·cm) and potential window (3.43 V). In addition, the surface state is changed from hydrogen termination to oxygen termination, so that the diamond grain has a positron affinity potential, and the electrochemical active area increases from 387 to 2893 μC/cm2. As the treatment time continues to extend to 20 min, the number of graphite layers on the surface of the film decreases, the diamond phase content increases, the resistivity of the film increases, and the electrochemically active area decreases. When the etching time reaches 25 min, the graphite layer under the composite film is exposed, and the graphite on the surface of the diamond is transformed into few-layer graphene, forming a double-layer structure of the top layer of few-layer graphene-coated diamond and the bottom layer of graphite, which synergistically improves the electrochemical activity (775 μC/cm2), reduces the resistivity of the composite film (1060.0 Ω·cm) and broadens the potential window (3.50 V). This work provides a novel plasma-etching strategy for fabricating diamond/graphene hybrid electrodes, and new insights into using the complementary advantages of these carbon allotropes for advanced electrochemical applications.
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图 1 氩/氧等离子体处理后NCD-G复合薄膜的表面形貌 (a) 0 min; (b) 5 min; (c) 10 min; (d) 15 min; (e) 20 min; (f) 25 min
Figure 1. Surface morphology of NCD-G composite films after argon/oxygen plasma treatment for different time: (a) 0 min; (b) 5 min; (c) 10 min; (d) 15 min; (e) 20 min; (f) 25 min.
图 2 氩/氧等离子体处理不同时间后NCD-G薄膜电极在不同溶液中的循环伏安i-E曲线 (a) 1 mol/L KCl溶液; (b) 0.001 mol/L [Fe(CN)6]3-/4-和1 mol/L KCl溶液
Figure 2. Cyclic voltammetry i-E curves of NCD-G thin film electrode in different solutions after argon/oxygen plasma treatment for different time: (a) 1 mol/L KCl solution; (b) 0.001 mol/L [Fe(CN)6]3-/4- and 1 mol/L KCl solutions.
图 3 (a) NCD-G薄膜在800—2200 cm–1范围的可见光Raman光谱及其拟合结果; (b) 2200—3500 cm–1范围Raman谱图; (c)—(e) 800—2200 cm–1可见光Raman光谱拟合后部分典型参数随着氩/氧混合等离子体处理时间的变化图
Figure 3. (a) Visible Raman spectra of NCD-G thin films in the range of 800–2200 cm–1 and their fitting results; (b) Raman spectra in the range of 2200–3500 cm–1; (c)–(e) some typical parameters of 800–2200 cm–1 visible Raman spectra with the treatment time of argon/oxygen mixed plasma.
图 4 低倍率高分辨透射电子显微镜图、局部放大图和对应的傅里叶变化图 (a)—(a2) NCD-G-T5; (b)—b2) NCD-G-T20; (c)—(c2) NCD-G-T25
Figure 4. Low power high-resolution TEM images, local magnification images and corresponding Fourier transform images: (a)–(a2) NCD-G-T5; (b)–(b2) NCD-G-T20; (c)–(c2) NCD-G-T25.
图 5 (a)氩/氧等离子体处理不同时间后NCD-G薄膜电极的C1s能谱; (b), (c) XPS拟合后部分典型参数随着热氧化处理时间的演化图
Figure 5. (a) The C1s spectra of NCD-G thin film electrode after argon/oxygen plasma treatment for different time; (b)–(c) evolution diagram of some typical parameters after XPS fitting with thermal oxidation treatment time.
表 1 氩/氧等离子体处理不同时间后NCD-G薄膜电极在1 mol/L KCl及0.001 mol/L Fe(CN)6]3-/4-溶液中的电化学性能参数
Table 1. Electrochemical performance parameters of NCD-G thin film electrodes in 1 mol/L KCl and 0.001 mol/L [Fe(CN)6]3-/4- solution after argon/oxygen plasma treatment for different time.
Sample Potential window/V Background
current/(mA·cm–2)Peak potential
difference ∆Ep/VElectrochemically
active area /(μC·cm–2)NCD-G-T0 3.32 14.41 0.041 387 NCD-G-T5 3.43 18.52 0.061 2893 NCD-G-T10 3.46 1.66 0.111 1272 NCD-G-T15 3.53 5.14 0.112 811 NCD-G-T20 3.56 1.44 — 257 NCD-G-T25 3.50 10.24 0.075 775 
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