Theory, experiment and computer simulation of the electrostatic potential at crystal/electrolyte interfaces
In this feature article we discuss recent advances and challenges in measuring, analyzing and interpreting the electrostatic potential development at crystal/electrolyte interfaces. We highlight progress toward fundamental understanding of historically difficult aspects, including point of zero potential estimation for single faces of single crystals, the non-equilibrium pH titration hysteresis loop, and the origin of nonlinearities in the titration response. It has been already reported that the electrostatic potential is strongly affected by many second order type phenomena such as: surface heterogeneity, (sub)surface transformations, charge transfer reactions, and additional potential jumps at crystal face edges and/or Schottky barriers. Single-crystal electrode potentials seem particularly sensitive to these phenomena, which makes interpretation of experimental observations complicated. We hope that recent theory developments in our research group including an analytical model of titration hysteresis, a perturbative surface potential expansion, and a new surface complexation model that incorporates charge transfer processes will help experimental data analysis, and provide unique insights into the electrostatic response of nonpolarizable single-crystal electrodes.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1004821
- Report Number(s):
- PNNL-SA-73319; 25629; KC0303020; TRN: US1101011
- Journal Information:
- Croatia Chemica Acta, 83(4):457-474, Vol. 83, Issue 4
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
COMPUTERIZED SIMULATION
ELECTRODES
ELECTROSTATICS
HYSTERESIS
MONOCRYSTALS
ORIGIN
SURFACE POTENTIAL
TITRATION
TRANSFER REACTIONS
TRANSFORMATIONS
single-crystal electrode
surface potential
Nernst potential
computer simulations
electron transfer
metal oxide
Environmental Molecular Sciences Laboratory