Effect of boron concentration and gas pressure on the electrochemical oxidation performance changes of HFCVD diamond films on Ti substrates
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摘要: 探究在热丝化学气相沉积生长硼掺杂金刚石的过程中，掺硼浓度与沉积气压对钛基硼掺杂金刚石薄膜的微观结构与电化学氧化性能的影响，并以四环素作为模拟污染物进行电化学氧化降解实验。使用扫描电子显微镜、拉曼光谱、紫外分光光度计以及电化学工作站对电极表面形貌、成分以及电化学性能进行表征。结果表明：随着掺硼浓度与沉积气压的增大，金刚石薄膜表面晶粒明显细化，生长速率下降；然而随着沉积气压的升高，金刚石的晶粒质量逐渐降低，但硼原子掺杂则会提高金刚石晶粒质量；在高掺硼浓度和低沉积气压的条件下，金刚石薄膜表面的硼原子浓度更高；高掺硼浓度和低沉积气压下所生成的较大晶粒尺寸和更高硼原子浓度的硼掺杂金刚石电极具有更优越的电化学性能、更高的降解效率以及更低的降解能耗。
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关键词:
- 钛基硼掺杂金刚石薄膜电极 /
- 电化学氧化 /
- 掺硼浓度 /
- 沉积气压 /
- 四环素
Abstract: The effects of boron concentration and deposition pressure on the microstructure and electrochemical oxidation performance of Ti/BDD electrodes during HFCVD growth were systematically investigated. The electrode's surface morphology, composition, and electrochemical performance were characterized by scanning electron microscope (SEM), Raman spectroscopy, ultraviolet spectrophotometry, and an electrochemical workstation. Tetracycline served as a simulated pollutant to evaluate the electrochemical oxidation degradation performance of BDD electrodes fabricated with different boron concentrations and deposition pressures. As air pressure increases, the grain quality of the diamond gradually decreases, yet boron atom doping enhances the grain quality of the diamond. Under high boron concentration and low pressure conditions, the boron atom concentration on the diamond film's surface is elevated. BDD electrodes with larger grain sizes and higher boron atom concentrations, prepared under these conditions, exhibit superior electrochemical performance, increased degradation efficiency, and reduced degradation energy consumption. -
图 1 不同掺硼浓度、沉积气压下的各样品表面SEM图
(a) 0-1 ；(b) 0-2 ；(c) 0-3 ；(d) 4-1 ；(e) 4-2 ；(f) 4-3； (g) 8-1 ；(h) 8-2 ；(i) 8-3
Figure 1. SEM images of each sample surface under different boron doping concentration and gas pressure
图 2 不同掺硼浓度、沉积气压下的各样品截面SEM图
(a) 0-1；(b) 0-2；(c) 0-3；(d) 4-1；(e) 4-2；(f) 4-3；(g) 8-1；(h) 8-2；(i) 8-3
Figure 2. SEM images of cross sections of samples under different boron concentration and gas pressure
图 3 不同掺硼浓度、沉积气压下的各样品 (a) 晶粒尺寸分布、(b) 生长速率
Figure 3. (a) Grain size distribution and (b) growth rate of various diamond films synthesized with different boron concentration and gas pressure
图 4 (a) 不同掺硼浓度、沉积气压下的金刚石薄膜的拉曼图；(b) 不同掺硼浓度下的BDD电极表面晶粒中的硼原子浓度
Figure 4. (a) Raman spectra of various diamond films synthesized with different boron concentration and gas pressure; (b) boron concentration of various BDD films synthesized with different boron concentration and gas pressure
图 6 在0.1 mol/L Na2SO4溶液中的各BDD电极CV曲线
(a) 4-1, (b) 4-2, (c) 4-3, (d) 8-1, (e) 8-2, (f) 8-3
Figure 6. CV curves of various BDD electrodes obtained in 0.1 mol/L Na2SO4 solution
图 7 开路电压处正负响应电流绝对值的平均值与扫速的线性拟合结果
(a) 4-1, (b) 4-2, (c) 4-3, (d) 8-3, (e) 8-3, (f) 8-3
Figure 7. Linear fitting result between average/absolute value of positive and negative response current at open circuit voltage and scan speed
图 8 不同BDD电极的拟合电化学阻抗图谱
Figure 8. Fitting electrochemical impedance spectroscopy of various BDD electrodes
图 9 不同BDD电极的 (a) TC移除率和(b) 能耗图
Figure 9. (a) TC removal rates and (b) energy consumption of various BDD electrodes
表 1 硼烷流量和沉积气压
Table 1. Boron flow rate and gas pressure
样品编号 硼烷流量 QB / sccm 沉积气压 p / kPa 0-1 0 1 0-2 0 2 0-3 0 3 4-1 0.4 1 4-2 0.4 2 4-3 0.4 3 8-1 0.8 1 8-2 0.8 2 8-3 0.8 3 
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表 2 HFCVD生长金刚石薄膜的沉积参数
Table 2. Synthesis parameters of various diamond films by HFCVD method
沉积参数 数值 热丝功率 P / W 560 基底温度 θ / ℃ 800±10 甲烷流量 QC / sccm 2 氢气流量 QH / sccm 98 丝底距 d / mm 14 沉积时间 t / h 5
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表 3 不同BDD电极的析氧电位与电势窗口参数
Table 3. Oxygen evolution potentials and potential windows of various BDD films
电极 析氧电位 u / V 电势窗口 U / V 4-1 2.69 3.40 4-2 2.70 3.48 4-3 2.59 3.42 8-1 2.72 3.55 8-2 2.69 3.53 8-3 2.68 3.53
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表 4 不同BDD电极的Cdl参数
Table 4. Cdl parameters of various BDD electrodes
电极 Cdl / μF 4-1 0.039 4-2 0.025 4-3 0.044 8-1 0.073 8-2 0.056 8-3 0.068
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表 5 不同BDD电极的EIS值
Table 5. EIS parameters of various BDD electrodes
电极 Rct / Ω Rs / Ω Rfilm / Ω Zw / Ω 4-1 19.9 7.2 12.0 0.02 4-2 18.0 7.4 12.2 0.02 4-3 25.0 7.1 12.6 0.02 8-1 13.3 7.0 13.7 0.02 8-2 13.2 6.6 13.1 0.02 8-3 21.5 6.6 13.0 0.02
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