Ocean College, Zhejiang University, Zhoushan 316021, China.
Second Institute of Oceanography, MNR, Hangzhou 310012, China.
ACS Sens. 2024 Oct 25;9(10):5234-5245. doi: 10.1021/acssensors.4c01403. Epub 2024 Sep 25.
The development of all-solid-state precise pH electrodes holds significant importance in various fields, particularly in marine scientific research. To achieve this goal, we proposed a novel fabrication technique for an all-solid-state ruthenium oxide (Ti/RuO) pH electrode. We thin-coated the RuCl precursor solution on a titanium wire substrate using a heat gun repeatedly and then calcined it in a mixture of LiCO and NaO at 400 °C to obtain a ruthenium oxide (RuO) film. This RuO film was subjected to acid treatment with dilute nitric acid, and a polytetrafluoroethylene heat shrink tube was wrapped around the non-RuO film area. Finally, the RuO film was fully immersed in a pH 4.00 buffer solution, finalizing the electrode preparation. The RuO film exhibits a dense and regular conical morphology. The Ti/RuO electrode demonstrates a good near-Nernstian response slope (e.g., -59.04 mV/pH at 25 °C), high linearity (e.g., = 0.9999), rapid response (<1 s), low hysteresis (<3 mV), excellent reversibility, and good repeatability in the pH range of 2.00-10.00. After full hydration, the Ti/RuO electrode shows a potential drift of 8.5 mV and a drift rate of approximately 0.27 mV/day over a period of 25 days, indicating good long-term stability. Furthermore, the Ti/RuO electrode exhibits robust resistance against interference from various ions and low-concentration redox substances, ensuring a long storage life (at least 280 days), and high measurement accuracy (e.g., ± 0.02 pH units) for diverse water samples, including seawater, freshwater, and tap water. This study has evaluated the potential of the Ti/RuO electrode as a reliable and accurate tool for pH measurements in marine scientific applications.
全固态精密 pH 电极的发展在各个领域都具有重要意义,特别是在海洋科学研究中。为了实现这一目标,我们提出了一种新型的全固态氧化钌(Ti/RuO)pH 电极制备技术。我们使用热喷枪将 RuCl 前体溶液反复涂覆在钛丝基底上,然后在 LiCO 和 NaO 的混合物中于 400°C 下煅烧,得到氧化钌(RuO)薄膜。将该 RuO 薄膜用稀硝酸进行酸处理,并用聚四氟乙烯热缩管包裹非 RuO 薄膜区域。最后,将 RuO 薄膜完全浸入 pH 4.00 缓冲溶液中,完成电极制备。RuO 薄膜呈现出致密且规则的锥形形态。Ti/RuO 电极表现出良好的近 Nernst 响应斜率(例如,在 25°C 时为-59.04 mV/pH)、高线性度(例如,=0.9999)、快速响应(<1 s)、低滞后(<3 mV)、优异的可逆性以及在 2.00-10.00 pH 范围内的良好重复性。在完全水合后,Ti/RuO 电极在 25 天的时间内显示出 8.5 mV 的电位漂移和约 0.27 mV/天的漂移速率,表明具有良好的长期稳定性。此外,Ti/RuO 电极对各种离子和低浓度氧化还原物质的干扰具有较强的抗干扰能力,具有较长的存储寿命(至少 280 天)和对包括海水、淡水和自来水在内的各种水样的高测量精度(例如,±0.02 pH 单位)。本研究评估了 Ti/RuO 电极作为海洋科学应用中可靠和准确 pH 测量工具的潜力。