Wu Tingjun, Kim Jiwon, Myung Nosang V
Department of Chemical and Environmental Engineering, University of California, Riverside, Riverside, CA, United States.
Laboratory of Advanced Functional Materials, Xiamen Institute of Rare-earth Materials, Haixi Institute, Chinese Academy of Sciences, Xiamen, China.
Front Chem. 2020 Mar 3;8:84. doi: 10.3389/fchem.2020.00084. eCollection 2020.
A systematic electrochemical study was conducted to investigate the reduction of tellurium (Te) in alkaline solutions. The effect of various parameters, including tellurite ion concentration, applied potential, and pH was investigated by both linear sweep voltammograms (LSVs) and electrochemical quartz crystal microbalance (EQCM). EQCM was essential to understand the reduction of Te(0) to soluble (-I) or Te(-II). The Tafel slopes for two Te reduction reactions [i.e., Te(IV) to Te(0) and Te(0) to Te(-I)] indicated that the electrochemical reduction of Te is strongly dependent on solution pH, whereas it is independent of the concentration of . At relatively weaker alkaline solutions (i.e., pH ≤ 12.5), the discharge of was determined to be the rate-limiting step during the reduction of Te(IV) to Te(0). For the reduction of Te(0) to Te(-I), the reaction follows a four-step reaction, which consisted of two discharge and two electrochemical reactions. The second discharge reaction was the rate-limiting step when pH ≤12.5 with the Tafel slope of 120 mV/decade. At a higher pH of 14.7, the Tafel slope was shifted to be 40 mV/decade, which indicated that the rate-limiting step was altered to the second electrochemical reaction. Te(0) deposits were found either on the surface of an electrode or in the solution depending on pH due to the different rate-limiting reactions, revealing that pH was a key parameter to dictate the morphology of the Te(0) deposits in alkaline media.
进行了一项系统的电化学研究,以探究碲(Te)在碱性溶液中的还原过程。通过线性扫描伏安图(LSV)和电化学石英晶体微天平(EQCM)研究了各种参数的影响,包括亚碲酸根离子浓度、施加电位和pH值。EQCM对于理解Te(0)还原为可溶性的(-I)或Te(-II)至关重要。两个Te还原反应[即Te(IV)还原为Te(0)和Te(0)还原为Te(-I)]的塔菲尔斜率表明,Te的电化学还原强烈依赖于溶液pH值,而与 的浓度无关。在相对较弱的碱性溶液(即pH≤12.5)中, 放电被确定为Te(IV)还原为Te(0)过程中的速率限制步骤。对于Te(0)还原为Te(-I),该反应遵循一个四步反应,包括两个放电和两个电化学反应。当pH≤12.5时,第二个放电反应是速率限制步骤,塔菲尔斜率为120 mV/十倍。在pH为14.7时,塔菲尔斜率变为40 mV/十倍,这表明速率限制步骤变为第二个电化学反应。由于速率限制反应不同,根据pH值的不同,Te(0)沉积物可在电极表面或溶液中形成,这表明pH值是决定碱性介质中Te(0)沉积物形态的关键参数。