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Interfacial microenvironments critically define reaction pathways for electrocatalytic processes through a combination of electric field gradients and proton activity. Non-aqueous ionic liquid electrolytes have been shown to sustain enhanced interfacial electric field gradients at intermediate ion concentration regimes of around 1 M, creating local environments that promote CO2 electroreduction. Notably, water at low concentrations absorbed by non-aqueous electrolytes is usually assumed to be the proton donor for CO2 reduction. Consumption of protons causes proton donors to become more negative by one unit charge, which significantly modifies the local concentration of charged species and hence should strongly impact local electric fields. Yet, how the coupling between proton donation and changing interfacial electric fields influences electrocatalytic processes in non-aqueous electrolytes remains largely unexplored. In this work, we show that the high activity of 1,3-dialkylimidazolium ionic liquids for CO2 reduction in acetonitrilebased electrolytes stems from the ability to act as cationic proton donors that release neutral conjugate bases. Using in situ electrochemical surface-enhanced Raman spectroscopy, we find that the formation of neutral conjugate bases from imidazolium cations preserves local electric field strengths at electrode-electrolyte interfaces, providing a powerful strategy to maintain an active local microenvironment for CO2 reduction. In contrast, conditions where water behaves as the primary proton donor generates [OH]- anions as negative “co-ions” in the electric double layer, which weakens the interfacial electric field and significantly compromises the steady-state CO2 reduction activity. Our study highlights that electrochemical driving forces are highly sensitive to the charge state of both reactant and product species and highlights the fact that the generation of interfacial co-ions plays a key role in determining electrochemical driving forces.
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Surface states of photoelectrodes by surface-specific steady-state and time-resolved sum frequency spectroscopies
The surface states of photoelectrodes as catalysts heavily influence their performance in photocatalysis and photoelectrocatalysis applications. These catalysts are necessary for developing robust solutions to the climate and global energy crises by promoting CO2 reduction, N2 reduction, contaminant degradation, and water splitting. The semiconductors that can fill this role are beholden as photoelectrodes to the processes of charge generation, separation, and utilization, which are in turn products of surface states, surface electric fields, and surface carrier dynamics. Methods which are typically used for studying these processes to improve semiconductors are indirect, invasive, not surface specific, not practical under ambient conditions, or a combination thereof. Recently, nonlinear optical processes such as electronic sum-frequency generation (ESFG) and second-harmonic generation (ESHG) have gained popularity in investigations of semiconductor catalysts systems. Such techniques possess many advantages of in-situ analysis, interfacial specificity, non-invasiveness, as well as the ability to be used under any conditions. In this review, we detail the importance of surface states and their intimate relationship with catalytic performance, outline methods to investigate semiconductor surface states, electric fields, and carrier dynamics and highlight recent contributions to the field through interface-specific spectroscopy. We will also discuss how the recent development of heterodyne-detected ESHG (HD-ESHG) was used to extract charged surface states through phase information, time-resolved ESFG (TR-ESFG) to obtain in-situ dynamic process monitoring, and two-dimensional ESFG (2D-ESFG) to explore surface state couplings, and how further advancements in spectroscopic technology can fill in knowledge gaps to accelerate photoelectrocatalyst utilization. We believe that this work will provide a valuable summary of the importance of semiconductor surface states and interfacial electronic properties, inform a broad audience of the capabilities of nonlinear optical techniques, and inspire future original approaches to improving photocatalytic and photoelectrocatalytic devices.
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- Award ID(s):
- 2045084
- PAR ID:
- 10577548
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- Chinese Journal of Chemical Physics
- Volume:
- 37
- Issue:
- 3
- ISSN:
- 1674-0068
- Page Range / eLocation ID:
- 376 to 397
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/1674-0068/cjcp2312133
