Beyond Recognition Chemistry: Ion Sensing through Intrinsic Electrochemical InterfacialResponse
- 1Department of Materials Science and Engineering, Delft University of Technology, Mekelweg 2, Groningen, AG, Netherlands, 9747
- 2Zernike Institute for Advanced Materials, Nijenborgh 3, Delft, Netherlands, 2628 CD
Abstract
Reliable ion sensing across multicomponent and dynamically changing environments is important in environmental monitoring, industrial process control, and biological analysis. In conventional electrochemical sensors, ion selectivity is typically achieved through redox reactions, ion-selective membranes, or molecular recognition layers, requiring ion-specific chemistry or materials to distinguish the target species. Yet dissolved ions also modify the intrinsic electrical structure of the electrode–electrolyte interface through differences in valence, hydrated size, mobility, polarizability, hydration energetics, and ion–surface interactions. These effects alter solvent organization, charge screening, ion accumulation, dielectric response, and transport within the electric double layer, creating composition-dependent electrical signatures without deliberately introduced receptors. Exploiting these intrinsic responses therefore offers an alternative basis for extracting ion-specific information from the interface itself. This review critically examines recognition-free ion sensing based on such intrinsic interfacial processes, with particular emphasis on non-Faradaic approaches. We first establish the physical origins of ion-dependent interfacial structure and examine how these differences are translated into measurable electrical responses, including capacitance, impedance, electronic channel modulation, ionic transport, and electrokinetic signals. The evolution of recognition-free sensing is then evaluated according to increasing analytical capability, from ion-dependent response and discrimination to single-analyte and multicomponent quantification. This analysis reveals that quantitative capability has advanced substantially, particularly through multidimensional electrical measurements and machine learning, but remains concentrated largely in simple solutions and controlled mixtures. Translation to complex and real matrices therefore represents a major unresolved frontier. Future progress will require deeper understanding of competitive multicomponent interfaces, deliberate control of interfacial properties, informative perturbation of the sensing environment, and data-driven analysis that remains connected to underlying physicochemical processes. Recognition-free sensing thus provides a route toward quantitative ion analysis in which analytical information is encoded by the interface itself rather than imposed exclusively through molecular recognition chemistry.
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BibTeX
@misc{armaki2026beyond,
title = {{Beyond Recognition Chemistry: Ion Sensing through Intrinsic Electrochemical InterfacialResponse}},
author = {Amir Mohseni Armaki and M. Ahmadi and A. Mol and P. Taheri and Amir Mohseni Armaki},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008976/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008976/v1},
note = {CC BY-NC},
}
RIS
TY - UNPB
TI - Beyond Recognition Chemistry: Ion Sensing through Intrinsic Electrochemical InterfacialResponse
AU - Amir Mohseni Armaki
AU - M. Ahmadi
AU - A. Mol
AU - P. Taheri
AU - Amir Mohseni Armaki
PY - 2026
DA - 2026/09/17
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008976/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008976/v1
AB - Reliable ion sensing across multicomponent and dynamically changing environments is important in environmental monitoring, industrial process control, and biological analysis. In conventional electrochemical sensors, ion selectivity is typically achieved through redox reactions, ion-selective membranes, or molecular recognition layers, requiring ion-specific chemistry or materials to distinguish the target species. Yet dissolved ions also modify the intrinsic electrical structure of the electrode–electrolyte interface through differences in valence, hydrated size, mobility, polarizability, hydration energetics, and ion–surface interactions. These effects alter solvent organization, charge screening, ion accumulation, dielectric response, and transport within the electric double layer, creating composition-dependent electrical signatures without deliberately introduced receptors. Exploiting these intrinsic responses therefore offers an alternative basis for extracting ion-specific information from the interface itself. This review critically examines recognition-free ion sensing based on such intrinsic interfacial processes, with particular emphasis on non-Faradaic approaches. We first establish the physical origins of ion-dependent interfacial structure and examine how these differences are translated into measurable electrical responses, including capacitance, impedance, electronic channel modulation, ionic transport, and electrokinetic signals. The evolution of recognition-free sensing is then evaluated according to increasing analytical capability, from ion-dependent response and discrimination to single-analyte and multicomponent quantification. This analysis reveals that quantitative capability has advanced substantially, particularly through multidimensional electrical measurements and machine learning, but remains concentrated largely in simple solutions and controlled mixtures. Translation to complex and real matrices therefore represents a major unresolved frontier. Future progress will require deeper understanding of competitive multicomponent interfaces, deliberate control of interfacial properties, informative perturbation of the sensing environment, and data-driven analysis that remains connected to underlying physicochemical processes. Recognition-free sensing thus provides a route toward quantitative ion analysis in which analytical information is encoded by the interface itself rather than imposed exclusively through molecular recognition chemistry.
ER -