炭黑/PTFE复合改性石墨毡阴极优化制备及高效电化学产H2O2机理研究

doi:10.11949/0438-1157.20250516

摘要/Abstract

摘要：

针对电芬顿技术中H₂O₂原位生成效率低的问题，该研究以优化制备的炭黑/聚四氟乙烯（CB/PTFE）复合改性石墨毡作为阴极构建了高效电化学合成H₂O₂的体系，并探究了操作条件对H₂O₂生成的影响规律及机制。在最优CB/PTFE质量比（1：5.5）与350 °C煅烧条件下，成功获得了材料的三维导电网络与疏水界面。研究发现，PTFE疏水层有效抑制了析氢副反应，CB增强了材料的电子传输能力，XPS结果证实改性后的材料具有更低的氧吸附能垒，SEM结果显示纳米活性位点均匀分布于材料表面。在0.09 A电流和0.6 L/min曝气量条件下，体系中H₂O₂生成浓度达338.87 mg/L，电流效率达92.7%。此外，所构建体系具有优异的抗离子干扰能力（Cl^-、SO₄^2-、NO₃^-浓度为300 mg/L时，H₂O₂浓度≥272 mg/L），5次循环使用后的H₂O₂生成量仅降低27.5%。研究结果为电化学合成H₂O₂提供了新型电极设计思路。

关键词: 炭黑, 聚四氟乙烯, 复合材料, 还原, 电化学, 过氧化氢

Abstract:

To address the low in‒situ H₂O₂ generation efficiency in electro‒Fenton technology, this study constructed an efficient electrochemical H₂O₂ synthesis system using an optimized carbon black/polytetrafluoroethylene (CB/PTFE) composite‒modified graphite felt cathode. The influence of operating conditions on H₂O₂ generation and underlying mechanisms were investigated. Under optimal CB/PTFE mass ratio (1:5.5) and calcination at 350 °C, a 3D conductive network and hydrophobic interface were successfully fabricated. The PTFE hydrophobic layer effectively suppressed the hydrogen evolution side reaction, while CB enhanced electron transfer capability. XPS confirmed reduced oxygen adsorption energy barriers on the modified material, and SEM revealed uniform distribution of nano‒active sites on the surface. At 0.09 A current and 0.6 L/min aeration rate, the H₂O₂ concentration reached 338.87 mg/L with 92.7% current efficiency. The system exhibited exceptional anti‒ion interference capability (maintaining H₂O₂ concentration ≥ 272 mg/L with 300 mg/L Cl^- SO₄^2-, and NO₃^-), and H₂O₂ production decreased by only 27.5% after 5 cycles of use. This work provides novel electrode design insights for electrochemical H₂O₂ synthesis

Key words: carbon black, polytetrafluoroethylene, composite materials, reduction, electrochemistry, hydrogen peroxide

中图分类号:

O646.54

刘玉灿, 宋汝佳, 徐心怡, 孙秀萍, 张岩, 王港, 杨晓永, 张岩香, 孙洪伟. 炭黑/PTFE复合改性石墨毡阴极优化制备及高效电化学产H₂O₂机理研究[J]. 化工学报, DOI: 10.11949/0438-1157.20250516.

Yucan LIU, Rujia SONG, Xinyi XU, Xiuping SUN, Yan ZHANG, Gang WANG, Xiaoyong YANG, Yanxiang ZHANG, Hongwei SUN. Optimized preparation of carbon black/PTFE composite-modified graphite felt cathode and the mechanism on high-efficiency electrochemical production of H₂O₂[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250516.

图/表 15

图1 不同CB与PTFE质量比时改性GF的LSV曲线(a)和CV曲线(b)

Fig.1 LSV curve (a) and CV curve (b) of modified GF with different CB/PTFE mass ratios

图2 CB/PTFE@GF的2e－ ORR与H2O2 RR反应的RRDE极化曲线(a)、RRDE H2O2选择性(b)和H2O2 RR选择性(c)

Fig.2 Polarization curves of the 2e－ ORR and H2O2 reduction reaction (RR) (a), H2O2 selectivity (b), and H2O2 RR selectivity (c) of CB/PTFE@GF

图3 200倍放大时GF (a)、CB/PTFE@GF (b)和CB/PTFE@GF使用120 min后(c)的SEM图；5000倍放大时GF (d)、CB/PTFE@GF (e)和CB/PTFE@GF使用120 min后(f)的SEM图

Fig.3 SEM images of GF (a), CB/PTFE@GF (b), and CB/PTFE@GF after 120 min of use (c) at 200× magnification; SEM images of GF (d), CB/PTFE@GF (e), and CB/PTFE@GF after 120 min of use (f) at 5000× magnification

图4 未改性GF与CB/PTFE@GF的XRD图(a)、XPS全谱图(b)、C1s谱图(c)、O1s谱图(d)、F1s谱图(e)

Fig.4 XRD patterns (a), XPS survey spectra (b), C1s spectra (c), O1s spectra (d), and F1s spectra (e) for GF and CB/PTFE@GF

图5 未改性GF与CB/PTFE@GF的FTIR图

Fig.5 FTIR spectra of GF and CB/PTFE@GF

图6 未改性GF、不同CB:PTFE比例改性GF、使用120 min后CB/PTFE@GF的接触角测试结果

Fig.6 Contact angle measurement results of GF, modified GF with different CB:PTFE mass ratios, and CB/PTFE@GF after 120 min of use

图7 CB加入量对H2O2生成量(a)和电流效率(b)的影响

Fig.7 Effect of CB loading amount on H2O2 production (a) and current efficiency (b)

图8 CB/PTFE比例对H2O2生成量(a)和电流效率(b)的影响

Fig.8 Effect of CB/PTFE mass ratio on H2O2 production (a) and current efficiency (b)

图9 煅烧温度对H2O2生成量(a)和电流效率(b)的影响

Fig.9 Effect of calcination temperature on H2O2 production (a) and current efficiency (b)

图10 电流对H2O2生成量的影响

Fig.10 Effect of current on H2O2 production

图11 曝气量对H2O2生成量的影响

Fig.11 Effect of aeration rate on H2O2 production

图12 初始溶液pH对H2O2生成量的影响

Fig.12 Effect of initial solution pH on H2O2 production

图13 共存离子对H2O2生成量的影响

Fig.13 Effect of coexisting ions on H2O2 production

图14 CB/PTFE@GF重复使用次数对H2O2生成量的影响

Fig.14 Effect of reuse cycles of CB/PTFE@GF on H2O2 production

图15 CB/PTFE@GF阴极电芬顿体系中四环素的去除率

Fig.15 Tetracycline removal efficiency in the CB/PTFE@GF cathode electro‒Fenton system

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炭黑/PTFE复合改性石墨毡阴极优化制备及高效电化学产H₂O₂机理研究

Optimized preparation of carbon black/PTFE composite-modified graphite felt cathode and the mechanism on high-efficiency electrochemical production of H₂O₂

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