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Operando Probing of Charge Transfer at the Semiconductor/Cocatalyst/Solution Interface in Photoelectrocatalytic Water
Deyun Zhang1,2, Zhongrui Min1,2, Yuran Li1,2
1State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China.
The Journal of Physical Chemistry Letters
|April 16, 2026
Summary
This study reveals how cocatalysts enhance photoelectrochemical (PEC) systems by dynamically adjusting interfacial potentials. This adaptive junction boosts efficiency and accelerates water oxidation, offering key insights into PEC performance.
Area of Science:
- Materials Science
- Electrochemistry
- Photocatalysis
Background:
- Efficient photoelectrochemical (PEC) systems require effective charge transfer at semiconductor/cocatalyst/solution interfaces.
- Probing these interfacial dynamics under operating conditions is crucial but challenging.
Purpose of the Study:
- To directly monitor electrochemical potentials at SrTiO3/CoOOH/water interfaces during PEC operation.
- To elucidate the mechanistic role of cocatalysts in promoting interfacial charge transfer.
Main Methods:
- Operando electrochemical potential monitoring at SrTiO3/CoOOH interfaces.
- Analysis of charge transfer dynamics and water oxidation kinetics.
Main Results:
- Hole transfer to CoOOH dynamically increases its electrochemical potential, creating an adaptive junction and enhancing photovoltage.
- CoOOH increases the water oxidation rate constant by 1.8x in a population-controlled regime.
- CoOOH induces a transition to a Butler-Volmer-controlled regime, exponentially increasing the water oxidation rate.
Conclusions:
- Cocatalysts like CoOOH play a vital role in facilitating charge transfer across multiple interfaces in PEC systems.
- Understanding these interfacial dynamics provides fundamental insights for designing more efficient PEC devices.
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