Measurement of total hydrogen content in hydrogen nanobubble water by headspace gas chromatography
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摘要:
氢气纳米气泡在环境修复、能源燃料和医疗健康等领域具有广泛的应用前景。目前氢气纳米气泡水中总氢含量的测定方法还相对有限，无法准确评定相关发生设备的性能。顶空气相色谱法通过加热使顶空瓶内体系达到气液平衡的方式将水样中的氢气转移到气相中，利用气相色谱仪来测定氢气纳米气泡水中的总氢含量。结果表明：样品的最佳平衡温度为50 ℃，平衡时间为15 min。通过对氢气纳米气泡水中氢气纳米气泡的数量浓度及粒径分布的检测，证实了该顶空气相色谱法适用于大多数纳米气泡产生方式所制备的氢气纳米气泡水体系，即氢气纳米气泡数量浓度范围为106~108个/mL，平均粒径范围为100~300 nm。当氢气纳米气泡数量浓度为6.7×106~3.8×108 个/mL时，对应测得的氢含量为0~3.12 mg/L，氢气纳米气泡数量浓度与对应氢含量变化一致，且能在2 min内完成检测。该方法简单高效，可以满足不同数量浓度氢气纳米气泡水的测试要求，为测定氢气纳米气泡水中总氢含量提供了可行的选择，有助于进一步研究氢气纳米气泡在各领域的重要应用并进行发生设备的性能评价。
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关键词:
- 氢气 /
- 氢气纳米气泡（HNBs） /
- 顶空气相色谱法 /
- 总氢含量
Abstract:Hydrogen nanobubbles have shown great potential in various applications such as environmental remediation, energy fuel production, and medical applications. However, accurately determining the total hydrogen content in hydrogen nanobubble water has been a challenge, which affects the evaluation of nanobubble generator performance. To address this issue, a method using headspace gas chromatography was developed, which transferred hydrogen from the liquid phase to the gas phase by heating the headspace bottle to achieve gas-liquid equilibrium, and then determined the total hydrogen content in hydrogen nanobubble water using gas chromatography. The results show that the optimal equilibrium condition for sample pretreatment is 50 ℃ for 15 min. It has been confirmed that the headspace gas chromatography method is suitable for analyzing a wide range of hydrogen nanobubble water systems (with number concentrations ranging from 106 to 108 mL−1 and average particle sizes ranging from 100 to 300 nm) prepared by most nanobubble generation methods, by detecting both number concentration and particle size distribution of hydrogen nanobubbles in hydrogen nanobubble water. When the number concentrations of hydrogen nanobubbles are within the range of 6.7×106-3.8×108 mL−1, the corresponding measured hydrogen contents fall between 0-3.12 mg/L. The changes in number concentrations of hydrogen nanobubbles are consistent with the corresponding hydrogen contents, and the detection process can be completed within 2 minutes. This method is simple and efficient, and can fulfill the test requirements regarding different number concentrations of hydrogen nanobubble water, providing a feasible option for quantifying the total hydrogen content in hydrogen nanobubble water. It facilitates further research on their significant applications of hydrogen nanobubbles in various fields and enables the evaluation of nanobubble generator performance.
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图 1 制备完成后的HNBs水静置过程中的溶液状态随时间变化
Figure 1. The state of HNBs solution changed with time during hydrostatic process after preparation
图 3 不同平衡温度和平衡时间对应的H2色谱峰面积
Figure 3. H2 chromatographic peak area of different equilibrium temperatures and equilibrium time
图 4 水中氢系列标准含量线性方程
Figure 4. Linear equation of hydrogen standard concentration in water
图 5 冷冻—真空脱气对HNBs水溶液中HNBs数量浓度及粒径的影响
Figure 5. Effect of freeze-vacuum degassing on number concentration and size of HNBs in solution
图 6 不同H2含量的HNBs水样的平行试验
Figure 6. Parallel tests of HNBs water with different hydrogen contents
编者按：微纳米气泡技术因其绿色、低碳和高效等特点近年来在天然水体修复、工业污水和尾水处理等方面展现出巨大的应用发展潜力。本刊特邀张立娟研究员、张现仁教授和李攀副教授作为专栏执行主编，策划“微纳米气泡研究与应用”特色研究专栏。该专栏从微纳米气泡的检测到近年来微纳米气泡在处理高盐废水、饮用水污染的效能与机制以及在膜污染和油气田废水的应用等方面进行了总结，为广大科研人员和企业提供微纳米气泡相关的研究和应用进展，有助于该领域的快速发展和助力打好碧水保卫战。 
张立娟，研究员，中国科学院上海高等研究院，博士生导师。现任中国颗粒学会微纳气泡专业委员会秘书长和全国微细气泡技术标准化技术委员会副秘书长等。主要研究方向是基于第三代先进同步辐射技术和纳米成像技术研究纳米气泡的物理性质及其在绿色清洗、环境、生物等方面的重要应用。发表SCI论文100余篇，其中以第一或通讯作者在Journal of the American Chemical Society和Environmental Science & Technology等发表纳米气泡相关论文80余篇。2020年获中国颗粒学会自然科学奖二等奖，2021年获陕西高等学校科技技术奖二等奖，2017年入选嘉定区第十三批高层次创新创业和急需紧缺人才等。主持1项和参与6项微细气泡国际标准的编写工作。 
张现仁，教授，北京化工大学，博士生导师。现任中国颗粒学会常务理事、中国颗粒学会微纳气泡专业委员会副主任、全国专业标准化技术委员会委员等。发表SCI论文180余篇。研究方向为纳微液滴和气泡的行为、热力学基础理论和计算流体力学等。 
李攀，副教授，同济大学，博士生导师。现任中国颗粒学会微纳气泡专业委员会副主任委员。近20年围绕微纳米气泡技术开展了气泡发生和应用技术研究，在水环境生态修复、水污染治理和绿色清洗技术上取得了一系列成果，并成功应用于工程实践。参编4本微纳米气泡科技书籍，主持2项微纳米气泡ISO国际标准和3项国家标准制定。开发的纳米气泡发生技术荣获2020年上海市科技进步奖一等奖（排名第6）。 
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表 1 不同HNBs水体系的平衡温度和平衡时间
Table 1. Test conditions for different number concentrations of HNBs
HNBs数量浓度/
（个/mL）HNBs平均
粒径/nm平衡温
度/℃平衡时间/
min6.7×106 247.2 50 10 6.4×107 270.6 50 10 3.8×108 144.6 50 10
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表 2 不同仪器和样品的测试条件对比
Table 2. Comparison of test conditions for different instruments and samples
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表 3 理论H2含量与顶空气相色谱法实际测得H2含量对比
Table 3. Comparison between theoretical H2 contents and actual H2 contents measured by headspace gas chromatography
H2含量理
论值/（mg/L）H2含量测定值/（mg/L） 加标回收
率/%第1次 第2次 第3次 平均值 0.160 0.152 0.166 0.142 0.153 95.833 0.802 0.706 0.737 0.759 0.734 91.521 1.603 1.678 1.439 1.578 1.565 97.629
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