自发的H2O2 在O2下积累,由NiS2的牺牲氧化驱动,没有外部电气/光子输入
Yu-Le Wang1, Cong Wang2, Song-Hai Wu1
1Tianjin Key Laboratory of Chemical Process Safety and Equipment Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P. R. China.
Langmuir : the ACS journal of surfaces and colloids
|October 3, 2025
概括
二碳酸盐 (HCO3-) 从二硫化 (NiS2) 的牺牲氧化中显著增加过氧化 (H2O2) 的产生. 这发生在通过中介氧的减少,碳酸作为水相比优越的捐赠者.
科学领域:
- 材料科学 材料科学 材料科学
- 电化学 电化学 电化学
- 环境化学环境化学
背景情况:
- 已知在有氧条件下通过金属二硫化物 (例如NiS2) 的牺牲性氧化自发的过氧化 (H2O2) 积累.
- 碳酸 (HCO3-) 在调节H2O2生产中的确切作用在机理上尚不清楚.
研究的目的:
- 阐明二碳酸盐对NiS2.2产生H2O2的影响机制.
- 调查二碳酸盐作为 donor 在氧的2e-降解中的作用.
主要方法:
- 在二碳酸盐的存在下,对NiS2进行电化学分析以研究氧气的减少.
- 电子磁共振 (EPR) 和拉曼光谱法用于识别反应中间体.
- 密度函数理论 (DFT) 计算,以评估抽取路径的热力学有利性.
主要成果:
- 二碳酸盐在NiS2上显著加速H2O2的产生,产量从53.85到90.12μM增加,在pH值9.0的0-0.5M二碳酸盐下,产量从53.85到90.12μM增加.
- 电化学数据表明二碳酸盐介导了2e-在NiS2.2.上将O2降解为H2O2的过程.
- EPR和拉曼分析确定了关键的表面中间体 (Ni-OO•和Ni-OOH),并证实碳酸是主要的H捐赠体.
结论:
- 双碳酸盐作为有效的捐赠剂,促进通过从二碳酸盐而不是从水中提取H的H2O2生产.
- 这项研究阐明了二碳酸盐在自发H2O2生成过程中,在没有外部能量输入的情况下,从NiS2牺牲氧化过程中发挥的机械重要性.
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