English

Operando Electrochemical UV-Vis Absorption Spectroscopy with Microsecond Time Resolution

• Ruifang Wei ^{1, 2,} ,
• Dongfeng Li ^{2, 3,} ,
• Heng Yin ^2, ,
• Xiuli Wang ^{2, ,} ,
• Can Li ^{1, 2, 3, ,}

• 1.

  Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China

• 2.

  State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

• 3.

  University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Email: xiuliwang@dicp.ac.cn (X.W.); Tel.: +86-411-84379027 (X.W.); Email: canli@dicp.ac.cn (C.L.). +86-411-84379070 (C.L.)

• Received Date: 15 July 2022
  Accepted Date: 05 September 2022
  Revised Date: 22 August 2022
  Available Online: 15 February 2023
• Fund Project:

  the National Key R & D Program of China 

  the DICP Foundation of Innovative Research 

Abstract: Operando spectroscopic characterization is effective for examining electrocatalytic reaction mechanisms. However, most operando characterization techniques currently used are based on (quasi-)steady-state spectroscopy, which often cannot directly measure transient changes occurring on the micro-millisecond time scale. Herein, an operando electrochemical UV-Vis absorption spectroscopy with 3 μs time resolution was realized by introducing bias pulses and synchronizing the bias pulse and spectral signals. Comparing the time-dependence curves of the bias pulse, collected spectral curve, and controlling voltage, a good time consistence for the three signals was observed, demonstrating the time-resolved ability of the novel apparatus. More importantly, two oxidation reactions, water oxidation reaction and hole sacrifice reagent oxidation reaction, showed distinct dynamics, verifying the reliability of the time-resolved kinetics. The water oxidation kinetics on a ferrihydrite (Fh) electrocatalyst were studied by this novel operando spectroscopic system. Different water oxidation steps were decoupled by analyzing the accumulation and decay dynamics of the operando time-resolved UV-Vis absorption data with various pulse widths and magnitudes of applied bias. A long bias pulse with width above 1s enabled the continuous accumulation of reaction intermediates in Fh electrocatalyst to reach a quasi-equilibrium state with electron extraction into the external circuit. In addition, a fast decay for water oxidation was observed after the applied bias was turned off. Importantly, when a short bias pulse with tens of ms width was applied, an abnormal intermediate accumulation process was observed after the applied bias was shut off, revealing a spontaneous species transformation process. These results confirm the validity of this novel method for examining species transformation kinetics at a fast timescale. The formation, transformation, and reaction kinetics of water oxidation reaction intermediates were directly studied on a µs to s time scale. Therefore, operando electrochemical UV-Vis absorption spectroscopy with µs time resolution can promote the understanding of various electrocatalytic reaction mechanisms and be used to guide the design and synthesis of novel high-efficiency electrocatalysts.

Key words:
• Electrocatalysis
•  /  Operando electrochemistry
•  /  UV-Vis absorption spectroscopy
•  /  Bias pulse
•  /  Time-resolved

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