磁场效应对理解水分解反应物的可能意义

doi:10.1016/S1872-2067(21)63821-4

催化学报 ›› 2022, Vol. 43 ›› Issue (1): 148-157.DOI: 10.1016/S1872-2067(21)63821-4

磁场效应对理解水分解反应物的可能意义

魏超^a, 徐梽川^a^,^b^,^c^,^*()

^a南洋理工大学材料科学与工程学院, 新加坡
^b南洋理工大学能源研究所, 新加坡
^c新加坡-耶路撒冷希伯来大学研究与创业联盟, 卓越研究与科技创业园, 新加坡

收稿日期:2021-03-18 接受日期:2021-04-01 出版日期:2022-01-18 发布日期:2021-04-29
通讯作者: 徐梽川

The possible implications of magnetic field effect on understanding the reactant of water splitting

Chao Wei^a, Zhichuan J. Xu^a^,^b^,^c^,^*()

^aSchool of Materials Science and Engineering, Nanyang Technological University, Singapore
^bEnergy Research Institute, Nanyang Technological University, Singapore
^cSingapore-HUJ Alliance for Research and Enterprise, NEW-CREATE Phase II, Campus for Research Excellence and Technological Enterprise (CREATE), Singapore

Received:2021-03-18 Accepted:2021-04-01 Online:2022-01-18 Published:2021-04-29
Contact: Zhichuan J. Xu
About author:* E-mail: xuzc@ntu.edu.sg
Zhichuan J. Xu is a Professor of Electrochemistry in the School of Materials Science and Engineering, Nanyang Technological University. He received his Ph.D. degree in Electroanalytical Chemistry in 2008 and B.S. degree in Chemistry in 2002 from Lanzhou University, China. His Ph.D. training was received in Lanzhou University (2002-2004), Institute of Physics, CAS (2004-2005), and Brown University (2005-2007). Since 2007, he worked at the State University of New York at Binghamton as a Research Associate and from 2009 he worked at the Massachusetts Institute of Technology as a Postdoctoral Researcher. Prof. Xu is a member of the International Society of Electrochemistry, The Electrochemistry Society, and a Fellow of the Royal Society of Chemistry. He serves as the president of the ECS Singapore Section. He was awarded the Zhaowu Tian Prize for Energy Electrochemistry by the International Society of Electrochemistry in 2019. He has been a Highly Cited Researcher ranked by Clarivate Analytics, Web of Science since 2018. His major research interest is electrocatalysis. He joined the Editorial Board of Chinese Journal of Catalysis in 2020.

摘要/Abstract

摘要：

电催化水分解由两个基元反应构成, 即析氢反应(HER)和析氧反应(OER). 开发强大的HER和OER技术需要在分子层面理解反应机理, 然而, 目前水分解反应的反应物还没有完全确定. 本文利用磁场来研究HER中的质子传输和OER中的氢离子传输, 对确定HER和OER中真实的反应物具有重要意义. 磁场是改变离子等带电物质运动的一种有效工具, 例如, 在铜电沉积中, 磁场改善了Cu²⁺在电极附近的迁移. 然而, 施加磁场对不同pH下的HER或OER速率没有影响, 这挑战了带电物种(即质子和氢氧化离子)作为反应物的传统观点. HER和OER对磁场的这种异常反应, 以及质子和氢氧根离子的传输遵循Grotthuss机制的事实, 都表明水可能是HER和OER在不同pH值下的通用反应物. 磁场研究结果表明, 水可能是HER和OER中的反应物, 也可能是其他涉及质子化和脱质子化步骤的电催化反应中的反应物. 综上, 在复杂的电解质相模型中, 只有充分考虑水的作用, 才能充分反映水电解质中HER和OER的电化学.

关键词: 电催化, 水分解反应, 磁场效应, 洛仑兹力, 金属沉积

Abstract:

Electrochemical water splitting consists of two elementary reactions i.e., hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Developing robust HER and OER technologies necessitates a molecular picture of reaction mechanism, yet the reactants for water splitting reactions are unfortunately not fully understood. Here we utilize magnetic field to understand proton transport in HER, and hydroxide ion transport in OER, to discuss the possible implications on understanding the reactants for HER and OER. Magnetic field is a known tool for changing the movement of charged species like ions, e.g. the magnetic-field-improved Cu²⁺ transportation near the electrode in Cu electrodeposition. However, applying a magnetic field does not affect the HER or OER rate across various pH, which challenges the traditional opinion that charged species (i.e. proton and hydroxide ion) act as the reactant. This anomalous response of HER and OER to magnetic field, and the fact that the transport of proton and hydroxide ion follow Grotthuss mechanism, collectively indicate water may act as the universal reactant for HER and OER across various pH. With the aid of magnetic field, this work serves as an understanding of water might be the reactant in HER and OER, and possibly in other electrocatalysis reactions involving protonation and deprotonation step. A model that simply focuses on the charged species but overlooking the complexity of the whole electrolyte phase where water is the dominant species, may not reasonably reflect the electrochemistry of HER and OER in aqueous electrolyte.

Key words: Electrocatalysis, Water splitting, Magnetic field, Lorenz force, Metal deposition

魏超, 徐梽川. 磁场效应对理解水分解反应物的可能意义[J]. 催化学报, 2022, 43(1): 148-157.

Chao Wei, Zhichuan J. Xu. The possible implications of magnetic field effect on understanding the reactant of water splitting[J]. Chinese Journal of Catalysis, 2022, 43(1): 148-157.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63821-4

https://www.cjcatal.com/CN/Y2022/V43/I1/148

图/表 6

Fig. 1. The schematic illustration of the experimental setup for applying a magnetic field during electrochemical measurement.

Fig. 2. (a) CV of Cu electrodeposition at polycrystalline Cu electrode. Data was collected in an electrolyte containing 0.5 M H2SO4 + 0.5 M CuSO4 with a scan rate of 10 mV/s for 3 consecutive CV cycles. The 1st and 3rd cycle were at ambient and the 2nd was under a magnetic field of 0.53 T. (b) Chronoamperometry (CA) of Cu electrodeposition at polycrystalline Cu electrode under a magnetic field with different applied potentials. The potential is not iR-corrected. (c) The schematic illustration of the effect of magnetic field (B) on the thickness of diffusion layer under a current flow (j). C* denotes the concentration of electroactive species as a function of the distance from the electrode surface, and a concentration gradient exists in the diffusion layer with a thickness of δd. The magnetic field induces a tangential flow (U), which leads to the formation of a hydrodynamic boundary layer with a thickness of δh. The velocity of U changes from U0 (the value in the bulk stream) to zero within the hydrodynamic boundary layer. The diffusion layer thickness under a magnetic field is δd-B.

Fig. 3. CA of Cu electrodeposition at polycrystalline Cu electrode in 0.5 M H2SO4 + 0.5 M CuSO4 with an applied potential of -0.4 V vs. RHE (not iR-corrected).

Fig. 4. Positive-going polarization curves (a) and CA (b) of HER at commercial Pt/C (40 wt%, Premetek) in electrolytes with different pH values: 0.1 M HClO4, 0.1 M KHCO3 and 0.1 M KOH. The catalyst loading is 2 µgPt/disk (disk area 0.196 cm2). Data was collected at ambient (blue dashed line) and under a magnetic field of 0.53 T (red solid line). The polarization curve was collected with a scan rate of 10 mV/s. During the CA measurement, the 0.53 T magnetic field was applied at the time indicated by the red arrow.

Fig. 5. CV (a) and CA (b) of OER at commercial IrO2 (Sigma-Aldrich, 2.77 m2/g according to Ref. [39]) in electrolytes with different pH values: 0.1 M HClO4, 0.1 M KHCO3 and 0.1 M KOH. The catalyst loading is 48 µgOxi/disk (disk area 0.196 cm2). Data was collected at ambient (blue dashed line) and under a magnetic field of 0.53 T (red solid line). The CV data was collected with a scan rate of 10 mV/s. During the CA measurement, the 0.53 T magnetic field was applied at the time indicated by the red arrow.

Fig. 6. The schematical illustration of Grotthuss mechanism, where proton (a) and hydroxide ion (b) transports along the hydrogen-bonded network in water. The proton (or hydroxide ion) diffuses from left to right. The dash line denotes the hydrogen bond and the arrow denotes the direction of proton diffusion. From top to bottom: it shows the four steps of proton (or hydroxide ion) diffusion along the exemplary four water molecules. Bottom: (a) the hydrogen evolution reaction, which takes the gray hydrogen atom for producing hydrogen gas; (b) the oxygen evolution reaction, which takes the gray oxygen atom for producing oxygen gas.

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磁场效应对理解水分解反应物的可能意义

The possible implications of magnetic field effect on understanding the reactant of water splitting

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