Experimental study on the determination of trace hydrogen peroxide in ultrapure water by gasometric method

doi:10.19965/j.cnki.iwt.2025-0205

Abstract

Abstract:

In the ultrapure water polishing system, the trace H₂O₂ produced by vacuum ultraviolet radiation will accelerate the degradation and aging of the downstream process polymer materials. Therefore, online determination of trace H₂O₂ has become a necessary measure to ensure system operation and control of micro-contamination. A new gasometric method based on hydrogen-oxygen synthesis reaction was developed, which analyzed the concentration of H₂O₂ in ultrapure water flowing through the reactor by measuring the mass concentration of H₂ and O₂ at the inlet and outlet of the hydrogenation reactor. Specifically, the palladium-loaded ion exchange resin was selected as the catalyst packed in the reactor, and H₂ and O₂ were highly selective for heterogeneous catalytic hydrogenation on the palladium metal surface. The results showed that the detection limit of the sample blank experiment was as low as 0.22 μg/L. The control experiment showed that the relative error between the measured value and the reference value was within 5%, with a strong linear correlation (R ²=0.999 8). The proposed determination method could not only provide an effective approach for the quantitative analysis of micro-contamination H₂O₂ in the ultrapure water of semiconductor advanced processes, but also provide a design method for constructing a new ultrapure water preparation system for deep removal of H₂O₂ and DO.

Key words: ultrapure water, hydrogen peroxide, micro-contamination, nanoparticles, gasometric method

摘要：

在超纯水精处理系统，由真空紫外线产生的痕量H₂O₂会加速下游工艺高分子材料的降解和老化，因此在线测定痕量H₂O₂成为保障系统运行与控制微污染的必要措施。开发了一种基于氢氧合成反应的新型气体计量法，通过测量氢化反应筒入口与出口H₂和O₂的质量浓度，可以分析流经反应筒的超纯水中H₂O₂的浓度。选择载Pd的离子交换树脂作为反应筒填充触媒，H₂和O₂在Pd金属表面高选择性发生多相催化加氢反应。结果表明，样本空白试验的检出限低至0.22 μg/L，对照试验显示测量值与参考值的相对误差在5%之内，具有较强的线性相关性（R ²为0.999 8）。测定方法不仅为半导体高端制程清洗水中微污染物H₂O₂的定量分析提供了有效手段，还为构建深度脱除H₂O₂和DO的新型超纯水制备系统提供了设计方法。

关键词: 超纯水, 过氧化氢, 微污染, 纳米粒子, 气体计量法

CLC Number:

TU991.2

Wei ZHENG, Dongli WU, Xin WEN, Jiahui XUE, Che LIU, Yingjie SHEN. Experimental study on the determination of trace hydrogen peroxide in ultrapure water by gasometric method[J]. Industrial Water Treatment, 2026, 46(1): 168-177.

郑伟, 吴东利, 温鑫, 薛佳卉, 刘澈, 申颖洁. 气相测定超纯水中痕量过氧化氢的试验研究[J]. 工业水处理, 2026, 46(1): 168-177.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0205

https://www.iwt.cn/EN/Y2026/V46/I1/168

Figures/Tables 13

References 44

[1]	郑伟，何丽华，温鑫，等. 7 nm/5 nm半导体工厂工艺设备用水研究报告［C］//松山湖先进半导体联合创新中心重点专项课题研究论文集. 北京：中国电子工程设计院股份有限公司，2023：205-232.
	ZHENG Wei， HE Lihua， WEN Xin，et al. Research report on water use for 7 nm/5 nm semiconductor factory process equipment［C］//Collection of Research Papers on Key Special Projects of Songshan Lake Advanced Semiconductor Joint Innovation Center. Beijing：China Electronics Engineering Design Institute Co.，Ltd.，2023：205-232.
[2]	SILLANPÄÄ M， NCIBI M C， MATILAINEN A. Advanced oxidation processes for the removal of natural organic matter from drinking water sources：A comprehensive review［J］. Journal of Environmental Management，2018，208：56-76. doi:10.1016/j.jenvman.2017.12.009
[3]	LI Mengkai， QIANG Zhimin， HOU Pin，et al. VUV/UV/chlorine as an enhanced advanced oxidation process for organic pollutant removal from water：Assessment with a novel mini-fluidic VUV/UV photoreaction system（MVPS）［J］. Environmental Science & Technology，2016，50（11）：5849-5856. doi:10.1021/acs.est.6b00133
[4]	T/ CECS 2010—2025 电子工业超纯水紫外线降解总有机碳系统技术规程［S］. doi:10.1021/acsestengg.1c00394.s001
	T/ CECS 2010—2025 Technical specification for total organic carbon ultraviolet degradation system in ultrapure water for electronics industry［S］. doi:10.1021/acsestengg.1c00394.s001
[5]	YANO D， MURAYAMA M， TAKAHASHI M，et al. Inhibition of copper dissolution by removal of oxidants from rinsing water using noble metal catalysts［C］//Speech Collection of the 61st Spring Academic Lecture of the Society of Applied Physics. Tokyo：Public Welfare Society of Applied Physics，2014（1）：2656. doi:10.1149/ma2013-02/30/2113
[6]	福井长雄，宫崎洋一. 純水製造方法及び装置：JP2015093226A［P］. 2015-05-18.
[7]	SEMI F63—1224 Guide for ultrapure water used in semiconductor processing ［S］. doi:10.1520/d7980-15
[8]	许淑芬，郑展望，徐甦. 国内外液相过氧化氢的测定方法及其进展［J］. 中国安全科学学报，2007，17（3）：166-170.
	XU Shufen， ZHENG Zhanwang， XU Su. Measuring method for hydrogen peroxide in liquid phase and its progress at home and abroad［J］. China Safety Science Journal，2007，17（3）：166-170.
[9]	陈亚红，刘红梅，田丰收，等. 酶催化分光光度法测定过氧化氢［J］. 理化检验-化学分册，2009，45（4）：401-403.
	CHEN Yahong， LIU Hongmei， TIAN Fengshou，et al. Enzyme catalytic spectrophotometric determination of hydrogen peroxide［J］. Physical Testing and Chemical Analysis（Part B（Chemical Analysis）），2009，45（4）：401-403.
[10]	汤亚芳，蒋治良，梁爱惠，等. 铜催化过氧化氢氧化纳米银-原子吸收光谱法测定过氧化氢［J］. 冶金分析，2009，29（3）：37-40.
	TANG Yafang， JIANG Zhiliang， LIANG Aihui，et al. Determination of hydrogen peroxide by atomic absorption spectrometry based on copper catalytic action on oxidation of nano-silver by hydrogen peroxide［J］. Metallurgical Analysis，2009，29（3）：37-40.
[11]	谭建忠. 电位滴定法测定过氧化氢溶液中的过氧化氢含量［J］. 合成纤维工业，2021，44（1）：83-86.
	TAN Jianzhong. Potentiometric titration determination of hydrogen peroxide content in hydrogen peroxide solution［J］. China Synthetic Fiber Industry，2021，44（1）：83-86.
[12]	ZAKARIA A B M， LESZCZYNSKA D. Novel design of non-enzymatic sensor for rapid monitoring of hydrogen peroxide in water matrix［J］. Journal of Electroanalytical Chemistry，2016，766：30-36. doi:10.1016/j.jelechem.2016.01.027
[13]	OHURA H， IMATO T， YAMASAKI S，et al. Potentiometric flow-injection determination of trace hydrogen peroxide based on its induced reaction in iron（Ⅲ）-iron（Ⅱ） potential buffer containing bromide and molybdenum（Ⅵ）［J］. Talanta，1996，43（6）：943-950. doi:10.1016/0039-9140(96)01840-1
[14]	TAHIROVIĆ A， ČOPRA A， OMANOVIĆ-MIKLIČANIN E，et al. A chemiluminescence sensor for the determination of hydrogen peroxide［J］. Talanta，2007，72（4）：1378-1385. doi:10.1016/j.talanta.2007.01.072
[15]	LI Jianzhong， DASGUPTA P K. Measurement of gaseous hydrogen peroxide with a liquid core waveguide chemiluminescence detector［J］. Analytica Chimica Acta，2001，442（1）：63-70. doi:10.1016/s0003-2670(01)01102-3
[16]	YAMASHIRO N， UCHIDA S， SATOH Y，et al. Determination of hydrogen peroxide in water by chemiluminescence detection，（Ⅰ）［J］. Journal of Nuclear Science and Technology，2004，41（9）：890-897. doi:10.1080/18811248.2004.9715561
[17]	ZOU Jing， CAI Huahua， WANG Daiyao，et al. Spectrophotometric determination of trace hydrogen peroxide via the oxidative coloration of DPD using a Fenton system［J］. Chemosphere，2019，224：646-652. doi:10.1016/j.chemosphere.2019.03.005
[18]	LIN Entian， WENG Qiaoling. Method and apparatus for determining concentration of compound in ultrapure water：US20240027411A1［P］. 2024-01-25.
[19]	森田博志，港康晴. 過酸化水素除去方法及び装置：JP6451824B2［P］. 2018-07-12.
[20]	郑伟，杨光明，程星华，等. 一种气相定量测定亚ppb级污染物的方法：CN116380981A［P］. 2023-06-07.
[21]	SUNDSTROM G P. Systems and methods for measuring composition of water：US20210181167［P］. 2021-06-17.
[22]	郑伟，杨光明，程星华，等. 一种痕量微污染物的在线分析装置：CN202321604866.4［P］. 2023-06-21.
[23]	PLAUCK A， STANGLAND E E， DUMESIC J A，et al. Active sites and mechanisms for H₂O₂ decomposition over Pd catalysts［J］. Proceedings of the National Academy of Sciences of the United States of America，2016，113（14）：E1973-E1982. doi:10.1073/pnas.1602172113
[24]	郑伟. 超纯液相环境纳米金属催化降除多元微污染物特性与机理［J］. 给水排水，2024，60（1）：66-77.
	ZHENG Wei. Characteristics and mechanism of catalytic degradation of multiple micropollutants by nano-metals in ultra-pure water［J］. Water & Wastewater Engineering，2024，60（1）：66-77.
[25]	郑伟，杨光明，程星华，等. 一种精处理回路提纯水的的系统：CN115893769B［P］. 2023-05-18.
[26]	LANDON P， COLLIER P J， CARLEY A F，et al. Direct synthesis of hydrogen peroxide from H₂ and O₂ using Pd and Au catalysts［J］. Physical Chemistry Chemical Physics，2003，5（9）：1917-1923. doi:10.1039/b211338b
[27]	SAMANTA C. Direct synthesis of hydrogen peroxide from hydrogen and oxygen：An overview of recent developments in the process［J］. Applied Catalysis A：General，2008，350（2）：133-149. doi:10.1016/j.apcata.2008.07.043
[28]	CHOUDHARY V R， SAMANTA C. Role of chloride or bromide anions and protons for promoting the selective oxidation of H₂ by O₂ to H₂O₂ over supported Pd catalysts in an aqueous medium［J］. Journal of Catalysis，2006，238（1）：28-38. doi:10.1016/j.jcat.2005.11.024
[29]	GONG Xiaoxiao， LEWIS R J， ZHOU Song，et al. Enhanced catalyst selectivity in the direct synthesis of H₂O₂ through Pt incorporation into TiO₂ supported AuPd catalysts［J］. Catalysis Science & Technology，2020，10（14）：4635-4644. doi:10.1039/d0cy01079k
[30]	TIAN Pengfei， OUYANG Like， XU Xinchao，et al. Density functional theory study of direct synthesis of H₂O₂ from H₂ and O₂ on Pd（111），Pd（100），and Pd（110） surfaces［J］. Chinese Journal of Catalysis，2013，34（5）：1002-1012. doi:10.1016/s1872-2067(12)60537-3
[31]	BIASI P， MIKKOLA J P， STERCHELE S，et al. Revealing the role of bromide in the H₂O₂ direct synthesis with the catalyst wet pretreatment method（CWPM）［J］. AIChE Journal，2017，63（1）：32-42. doi:10.1002/aic.15382
[32]	郑伟，王文龙，倪卫斌，等. Ⅷ族过渡金属对电子级超纯水H₂O₂强化去除特性与研究进展［J］. 工业水处理，2024，44（7）：57-66.
	ZHENG Wei， WANG Wenlong， NI Weibin，et al.Enhanced removal characteristics and research progress of hydrogen peroxide in electronic grade ultrapure water by group Ⅷ transition metals［J］.Industrial Water Treatment，2024，44（7）：57-66.
[33]	郑伟，程星华，杨光明，等. 先进芯片制造用清洗水的提纯装置与方法：CN115626745A［P］. 2023-01-20.
[34]	SHOTA MORINO， DAISAKU YANO， YUKINARI YAMASHITA，et al. Measuring system and measuring method of hydrogen peroxide concentration：IN446995B［P］. 2023-08-25.
[35]	漆红兰，李佳妮，张成孝. 检出限与灵敏度关系及影响因素的探讨［J］. 大学化学，2021，36（9）：219-225. doi:10.3866/pku.dxhx202107008
	QI Honglan， LI Jiani， ZHANG Chengxiao. Discussion on the relationship and influence factors of the limit of detection and the sensitivity of analytical methods［J］. University Chemistry，2021，36（9）：219-225. doi:10.3866/pku.dxhx202107008
[36]	GB/T 5750.3—2023 生活饮用水标准检验方法第3部分水质分析质量控制［S］. doi:10.1007/978-3-319-04334-0_7
	GB/T 5750.3—2023 Standard examination methods for drinking water—Part 3：Water analysis quality control ［S］. doi:10.1007/978-3-319-04334-0_7
[37]	文慧，刘珣，张尚青，等. 比率荧光法传感pH检出限的探讨［J］. 分析化学，2019，47（4）：597-604.
	WEN Hui， LIU Xun， ZHANG Shangqing，et al. Discussion on definition of detection limit for ratio fluorescence pH sensing methods［J］. Chinese Journal of Analytical Chemistry，2019，47（4）：597-604.
[38]	靳晓婷. 分析化学中检出限与测定下限分析［J］. 化工设计通讯，2020，46（11）：71-72.
	JIN Xiaoting. Analysis of detection limit and determination limit in analytical chemistry［J］. Chemical Engineering Design Communications，2020，46（11）：71-72.
[39]	GB/T 27417—2017 合格评定化学分析方法确认和验证指南［S］. doi:10.3403/30496369
	GB/T 27417—2017 Conformity assessment—Guidance on validation and verification of chemical analytical methods ［S］. doi:10.3403/30496369
[40]	YAMASHIRO N， UCHIDA S， SATOH Y，et al. Determination of hydrogen peroxide in water by chemiluminescence detection，（Ⅰ）［J］. Journal of Nuclear Science and Technology，2004，41（9）：890-897. doi:10.1080/18811248.2004.9715561
[41]	郑伟，张婧宇，温鑫，等. 7 nm/5 nm半导体数字孪生工厂超纯水制备系统关键技术研究［C］//松山湖先进半导体联合创新中心重点专项课题研究论文集. 北京：中国电子工程设计院股份有限公司，2023：91-195.
	ZHENG Wei， ZHANG Jingyu， WEN Xin，et al. Research on key technologies of ultrapure water preparation system for 7 nm/5 nm semiconductor digital twin factory［C］//Collection of Research Papers on Key Special Projects of Songshan Lake Advanced Semiconductor Joint Innovation Center. Beijing：China Electronics Engineering Design Institute Co.，Ltd.，2023：91-195.
[42]	ZHANG Xinbo， YANG Yuanying， NGO H H，et al. A critical review on challenges and trend of ultrapure water production process［J］. Science of the Total Environment，2021，785：147254. doi:10.1016/j.scitotenv.2021.147254
[43]	OUYANG Wanyue， WANG Wenlong， ZHANG Yilin，et al. VUV/UV oxidation performance for the elimination of recalcitrant aldehydes in water and its variation along the light-path［J］. Water Research，2023，228：119390. doi:10.1016/j.watres.2022.119390
[44]	郑伟，温鑫，卢芳慧，等. 一种稳定输出半导体工艺用超纯水的调控方法和装置：CN119306359A［P］. 2025-01-14.

化学方程式	ΔH/（kJ· mol^-1）	ΔG ^θ/（kJ·mol^-1）	反应式序号
H₂+1/2O₂→H₂O	241.6	-237.2	（1）
H₂+O₂→H₂O₂	135.8	-120.4	（2）
H₂O₂→H₂O+1/2O₂	105.8	-116.8	（3）
H₂O₂+H₂→2H₂O	211.5	-353.8	（4）

化学方程式	ΔH/（kJ· mol^-1）	ΔG ^θ/（kJ·mol^-1）	反应式序号
H₂+1/2O₂→H₂O	241.6	-237.2	（1）
H₂+O₂→H₂O₂	135.8	-120.4	（2）
H₂O₂→H₂O+1/2O₂	105.8	-116.8	（3）
H₂O₂+H₂→2H₂O	211.5	-353.8	（4）

项目	开启MGA（吸收H₂）	开启MGA（解吸O₂）	关闭MGA
反应筒进口DO₁	7.9 mg/L	112.6 μg/L	7.9 mg/L
反应筒出口DO₂	7.8 mg/L	118.8 μg/L	7.9 mg/L
差值溶氢（Δ［DH］_1-2）	13.39 μg/L	0.10 μg/L	1.54 μg/L
差值溶氧（ΔDO_2-1）	100.16 μg/L	6.21 μg/L	无法获得
H₂O₂测定质量浓度	15.42 μg/L	15.53 μg/L	无法获得

项目	开启MGA（吸收H₂）	开启MGA（解吸O₂）	关闭MGA
反应筒进口DO₁	7.9 mg/L	112.6 μg/L	7.9 mg/L
反应筒出口DO₂	7.8 mg/L	118.8 μg/L	7.9 mg/L
差值溶氢（Δ［DH］_1-2）	13.39 μg/L	0.10 μg/L	1.54 μg/L
差值溶氧（ΔDO_2-1）	100.16 μg/L	6.21 μg/L	无法获得
H₂O₂测定质量浓度	15.42 μg/L	15.53 μg/L	无法获得

H₂质量浓度/（μg·L^-1）	S	RSD/%
0.05	0.011	22.00
0.08	0.009	10.75
0.12	0.010	8.21
0.20	0.014	7.15
0.31	0.018	5.89
0.49	0.019	3.92
0.78	0.016	2.11
1.23	0.024	1.97
1.95	0.044	2.24
3.08	0.045	1.47
4.86	0.054	1.11
7.68	0.071	0.92
12.14	0.102	0.84
19.13	0.151	0.79
29.98	0.225	0.75

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