电催化反应中的界面双电层：理论、表征与应用

doi:10.1016/j.actphy.2024.100041

摘要/Abstract

摘要：

界面双电层是电催化反应的核心区域。催化剂表面原子、反应物、中间体、产物、溶剂分子和离子等组分，共同构成了复杂的动态反应网络。这种特殊的组成和结构赋予界面双电层以特殊的性质，深刻地影响了电催化反应的路径与结果。本文将以电催化反应中的双电层为主要研究对象，围绕双电层理论模型及其历史沿革、双电层的实验表征方法和双电层对电催化反应的影响这三个方面，以若干电催化反应前沿研究为例，阐述双电层与电催化反应之间的关联，并介绍一些特定情形下电催化双电层研究的研究方法和研究逻辑。

关键词: 电催化, 双电层, 电极/电解液界面, 理论模型, 原位表征技术

Abstract:

The interfacial electrical double layer (EDL) is the interfacial space filled with a complex and dynamic reaction network forming by catalyst's surface atoms, reactants, intermediates, products, solvent molecules, ions, and other components. EDL has a profound impact on electrocatalytic reactions, affecting both the thermodynamics and kinetics of these processes. Manipulating the composition and structure of the EDL microenvironment sets an additional level of tuning toward the electrocatalysis, to the traditional catalyst optimization. It resembles the delicate manipulation of the environment around the active sites by protein scaffold in enzymes. However, the rational optimization of the EDL demands a deep understanding about its structure and dynamics. Problem lies in the complexities of interfacial EDL, which includes complicated multi-body interactions, few molecular-level characterization techniques, and scarce EDL modification strategies. In this tutorial, we delve into the intricacies of the interfacial EDL in electrocatalytic reactions, and seek to provide those who are new to this field a thorough summary of the theory, characterization, history, recent progresses within the regime of EDL for electrocatalysis. We begin by discussing the theoretical models that describe the structure and properties of EDL, including 4 classical EDL models, their applications in electrocatalytic analysis and modifications, and relevant calculation modulation methods. These models are arranged in the chronical order, such that a historical summary of how the EDL theory evolves from simple models to complicated details is provided. We then provide an overview of cutting-edge techniques in electrochemical measurement methods, in situ spectroscopic characterization techniques and scanning probe microscopy methods. Specifically, we aim to summarize the advantages and disadvantages of each technique, with an emphasis on their capability of probing the EDL region. The summary table can provide junior students a quick overview and a useful tool for selecting the appropriate techniques toward addressing the EDL properties for electrocatalysis. Furthermore, by combining the theory and characterization techniques, we list several pivotal studies from the past five years emphasizing on the "electrode side interfacial modification" approach and "solution side interfacial modification" approach, toward modulating the EDL to optimize the electrocatalytic properties. These examples not only show the recent progresses in this field and offer fundamental details about how researchers in this field address the problems from the aspect of EDL. With these combined theory, characterization and research samples, we hope that the new-comings can gain interest to this field, sense the enormous opportunities and understand the general principles of EDL toward electrocatalysis.

Key words: Electrocatalysis, Electrical double layer, Electrode/electrolyte interface, Theoretical model, In situ characterization technique

曹雪婷, 察爽爽, 龚鸣. 电催化反应中的界面双电层：理论、表征与应用[J]. 物理化学学报, 2025, 41(5), 100041. doi: 10.1016/j.actphy.2024.100041

Xueting Cao, Shuangshuang Cha, Ming Gong. Interfacial Electrical Double Layer in Electrocatalytic Reactions: Fundamentals, Characterizations and Applications[J]. Acta Phys. -Chim. Sin. 2025, 41(5), 100041. doi: 10.1016/j.actphy.2024.100041

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2024.100041

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I5/100041

图/表 14

图1

表1

Symbols	Connotations
A	the interactions between adsorbates in the Frumkin adsorption isotherm
b	difference between the Gibbs free energy change for the formation of the down-state water at the electrode surface and the up-state water
β	symmetry factor
c_a	concentration of adsorbates in the bulk phase of the solution
c₀	concentration of species i in the bulk phase of the solution
$ c_{{Re} }^* $	concentration of the reduced species Re in the bulk phase of the solution in the interfacial single-electron transfer reaction
$ {c_{{\text{Ox}}}} $	concentration of the oxidized species Ox in the interfacial single-electron transfer reaction
$ c_{{\text{Ox}}}^{\text{*}} $	concentration of the oxidized species Ox in the bulk phase of the solution in the interfacial single-electron transfer reaction
c_surface	concentration of species on electrode surface
C	double layer (differential) capacitance
C_charge	capacitance formed when ions are adsorbed on the electrode surface
C_dipole	capacitance formed when water dipoles are adsorbed by the electrode
C_eqcm	correction constant for EQCM resonator
C_M	the contribution of electrode side to the interfacial capacitance
C_H	the contribution of Helmholtz layer to the interfacial capacitance
C_G	the contribution of diffusion layer to the interfacial capacitance
χ⁽²⁾	second-order optical susceptibility
χ⁽³⁾	third-order optical susceptibility
$ \chi _{{\text{eff}}}^{(2)} $	The effective second-order optical susceptibility
d	Differential notation (as distinguished from italicized d for the plate separation distance)
d	the plate separation distance in the parallel plate capacitor model
E	electric field intensity
e₀	the charge carried by one single electron
ε	the dielectric constant in a certain medium
ε₀	vacuum dielectric constant
F	Faraday constant
f	f= F/RT
Δf	the change in vibrational frequency measured by EQCM
ΔG_n	Gibbs free energy change for primitive reaction steps associated with n proton-electron pairs
$ \Delta g_{{\text{dipole}}}^{\text{S}} $	the change of surface dipole potential
g^M	the electrode potential on the metal electrode surface within the double layer
g^S	the electrode potential on the solution side within the double layer
$ g_{{\text{dipole}}}^{\text{S}} $	The surface potential contributed by oriented water molecules
I_2ω	the emitted light intensity of SHG
i	imaginary unit, species designation (such as species i)
i	current density
i₀	exchange current density
i_cath	cathodic current density
i_S	the current of the substrate in SECM
i_T	the (Faradaic) current passing through the tip in SECM
k₀	standard reaction rate constant
k_b	backward reaction rate constant
k_f	forward reaction rate constant
κ^-1	the characteristic thickness of the EDL in the GC model
K_A→B	the integral capacitance from A to B
γ	interfacial tension
k_B	Boltzmann constant
Δm	the change of the electrode mass
M_ads	the molar mass of adsorbed species
$ \overrightarrow \mu $	dipole moment
$ \mu _{\text{e}}^{\text{R}} $	the electrochemical potential of the electrons on the reference electrode
$ \mu _{\text{e}}^{{\text{M '}}} $	the electrochemical potential of the electrons on the (other) metal electrode
Δμ	Stark tunability
n	Variable indicating ‘number’, e.g., number of radical reactions, number of water molecules in hydrated ions, etc.
N_{e, trans}	electron transfer coefficient per unit mole of reaction
N_t	the background signal in a radiotracer measurement
N_t^’	the signal under the voltage without specific adsorption in a radiotracer measurement
N_t^’’	the signal under the voltage with specific adsorption in a radiotracer measurement
N_water	number of water molecules on the electrode surface
ϕ	the phase of emitted light of SHG
φ	inner potential, the electrode potential under certain conditions
Δφ	the potential difference within the electrical double layer, i.e., the electrode \| solution interface potential difference
φ_t	the potential of the working electrode at time t
φ_dc	the potential of the working electrode under direct current
φ_x	the potential at a distance x from the electrode surface, with the bulk solution potential defined as 0
ψ	outer potential
Δψ	the outer potential difference of the electrical double layer
ω	frequency
q_CA	the charge density of specific adsorbed ions
q_d	the total diffuse charge density in solution
q_M	the charge density of the (metal) electrode
ΔQ	the change of quantity of electric charge during electrocatalytic reactions
R	ideal gas constant
R	the roughness of the electrode
t	time
T	absolute temperature
θ_a	coverage (referring to the fraction of the surface that is covered)
θ	the phase difference between χ⁽³⁾ and χ⁽²⁾
U	Maximum value of dipole-dipole interaction energy
V	the voltage drop per unit area of M \| S EDL interface
V_app	applied potential
v_scan	the potential scan rate in cyclic voltammetry
x	the vertical distance of the target site from the electrode surface
X	the constant related to lateral interactions, 0 < X < 1
y	an artificially defined physical quantity to represent the electrical and lateral interactions in interactions within EDL
Z	an artificially defined physical quantity to represent the distribution of water in the up and down states on the electrode surface
z	the number of charges per ion

表1

图2

表2

Characterization Techniques	Abbreviation	Basic Principles	Vertical Resolution	Horizontal Resolution	Time Resolution	Information	On the Electrode Side	IHP/Adsorption Layer	OHP & Diffusion Layer	Category
Electrocapillary	–	Measurement of interfacial tension as a function of applied voltage	Macroscopic nature	Macroscopic nature		Measurement of the differential capacitance and the potential of zero charge of an EDL				Electrochemical Method
Cyclic Voltammetry	CV	Potential scanning cyclically to obtain the current-potential relationship	Macroscopic nature	Macroscopic nature		Electrochemical behaviors of the system				Electrochemical Method
Alternating Current Voltammetry	ACV	Relationship between the variation of AC amplitude and phase with DC polarization potential at a given electrical signal frequency	Macroscopic nature	Macroscopic nature		Distinguishing between Faraday and charging currents and separating to obtain information on different electrochemical processes				Electrochemical Method
Electrochemical Impedance Spectroscopy	EIS	Variation of AC impedance of an electrochemical system as a function of the frequency of an applied electrical signal under a certain condition of DC polarization	Macroscopic nature	Macroscopic nature	Frequency dependent, up to milliseconds	Solution resistance from reference electrode to working electrode, double layer capacitance, charge transfer resistance, detection of diffusion processes from the body to the electrode surface and in the electrolyte				Electrochemical Method
Electrochemical Quartz Crystal Microbalance	EQCM	The oscillation frequency of quartz crystal lenses is affected by changes in electrode mass, thus correlating electrochemical information with changes in electrode mass				Relationships between mass, current and charge as a function of potential in the surface layer of solid electrodes, tracking mass transfer and charge transfer processes				Derivative Electrochemical Method
Radiotracer Measurements	-	Detection of β particles from isotope decay in the electrolyte by means of a scintillation counter, where the signal from the decay of the radioactive substrate is not recorded if it is adsorbed on the electrode				Surface radiation intensity or surface concentration, corresponding to the number of molecules adsorbed on the electrode surface Limitations lie in finding target molecules with radioactive isotopes		√		Spectroscopy
in situ/operando Infrared Reflection Absorption Spectroscopy	IRRAS	The infrared light passes through a thin layer of electrolyte to illuminate the interface, while elective absorption occurs and multiple reflections and attenuation result in an outgoing light that contains information about the interface	100 nm	5 μm	In the order of milliseconds and microseconds	Chemical nature and adsorption structure of adsorbed species Orientation of molecules on surfaces and the effect of double layer electric fields on intramolecular bonding Functional groups, molecular symmetry, and catalyst-molecule interactions		(very weak)	√	IR Spectroscopy
Attenuated Total Reflectance Infrared Spectroscopy	ATR-IR	Infrared light irradiates the sample to be measured, penetrates into the interface to a certain depth and undergoes selective absorption, and is reflected and attenuated several times to obtain the outgoing light which contains the interface information	100 nm	5 μm			√	√ (no resolution)	√	IR Spectroscopy
Surface Enhanced Infrared Absorption Spectroscopy	SEIRAS	When a molecule is adsorbed on the surface of a noble metal, transition metal or semiconductor substrate, its infrared absorption signal is dramatically amplified by several orders of magnitude	10 nm	5 μm			√	√	√	IR Spectroscopy
in situ/operando Raman Spectroscopy	Raman	Scattered light undergoes an energy exchange within the illuminated object, and the difference in photon energy between the scattered light and the incident light reflects information about the vibrational energy levels of the molecules	500 nm	2-3 μm	Generally in the order of milliseconds with CCD; in the order of 10 nanoseconds with pump light	Structure and orientation of molecules on the surface, the effect of the electric field of the double electric layer on intramolecular bonding; qualitative and quantitative information about the electrode composition in the near-surface region, i.e., bonding on the catalyst surface; changes in the surface with potential, state of charge, and/or time	√	√ (no resolution)	√	Raman Spectroscopy
Surface enhanced Raman Spectroscopy	SERS	When a molecule is adsorbed on the surface of a noble metal, transition metal or semiconductor substrate, the Raman scattering signal is dramatically amplified by several orders of magnitude	1 nm				√	√	√	Raman Spectroscopy
Sum Frequency Generation Vibrational Spectroscopy	SFG-VS	Simultaneous irradiation of an electrochemical interface with non-central symmetry (satisfying symmetry breaking) by an infrared beam and a visible beam produces a sum-frequency signal				Measurement of surface potential, molecular structure, symmetry and orientation of interfacial reactants/solvents/intermediates, and surface number density	√	√	No solution phase information	Nonlinear Optical Characterization
Second Harmonic Generation	SHG	Two incident photons of the same frequency pass through the electrode-electrolyte interface to produce a doubled-frequency photon, and the resulting intensity of the incident light reflects the electric field information at the interface				Measurement of surface potential, determination of zero-charge potential, molecular structure and orientation of interfacial reactants/solvents/intermediates	√	√	No solution phase information	Nonlinear Optical Characterization
in situ X-ray Diffraction	XRD	Using an in situ electrochemical cell, X-rays diffract with the working electrode phase and contain information on the bulk phase of the crystalline electrode under reaction conditions	> 1 mm	1–3 μm	Fast enough to capture the typical dynamic processes of active substances in operando experiments	Qualitative and quantitative information on the (average) composition of bulk phase electrodes Changes in the crystal structure of bulk phase electrodes with potential, state of charge and/or time	√ (bulk)	×	×	X-Ray Diffraction Spectroscopy
in situ X-ray absorption near edge structure	XANES	Incident X-rays excite the inner electrons to unoccupied energy levels and the X-rays are strongly absorbed, reflecting information about the oxidation state and electronic structure of the element under test	Penetrate the bulk phase			Average oxidation states and electronic configurations of specific elements in electrode materials for amorphous electrodes	√ (bulk)	Characterization of hydrogen bond strength of water molecules in IHP	×	X-Ray Absorption Spectroscopy
in situ Extended X-ray Absorption Fine Structure	EXAFS	Incident X-ray excitation to the continuum state of the inner electrons interferes with neighboring atoms, reflecting information such as bond distances and coordination numbers	Penetrate the bulk phase	5 Å range of short-range covalent structures		Interface constituent element analysis, interatomic distances, coordination information, available for amorphous electrodes	√ (bulk)	× (analyzed indirectly in conjunction with other techniques)	×	X-Ray Absorption Spectroscopy
Ambient Pressure X-ray Photoelectron Spectroscopy	APXPS	Improvements to the vacuum system, X-ray source and feeding technique have enabled the XPS to be tested at near atmospheric pressure, measuring the photoelectron beam formed by the incident X-rays striking the inner electrons	1–12 nm	30 μm		Qualitative and semi-quantitative elemental analysis, depth imaging, oxidation states; molecular structure identification at interfaces	√	√	√	Photoelectron Spectroscopy
Ambient Pressure Resonance Auger Electron Spectroscopy	APRAES	The incident X-ray-excited inner electron leaps back into the inner vacancy and the energy released excites the valence electron, the Rochelle electron	1–6 nm	0.02–50 μm		Surface elemental composition, adsorbate coverage, interfacial electronic structure	√	√	√	Photoelectron Spectroscopy
Electrochemical Scanning Tunneling Microscopy	EC-STM	The tunnelling current is sensitive to the probe-sample distance and the electronic properties of the sample, reflecting interfacial information	0.1–1 nm	1–10 nm	In the order of milliseconds	Adsorption of species structure, electrode surface morphology, electronic structure and active sites, information on both liquid and solid phase sides can be obtained	√	√		Scanning Probe Microscopy
Scanning Electrochemical Microscopy	SECM	Faraday currents generated by electrochemical reactions at the interface, which are strongly correlated with the probe-sample distance, reflect interfacial information	10 nm	20–50 nm		Quantification of local concentrations of interfacial species, adsorbed species coverage, local pH, surface reactivity			√	Scanning Probe Microscopy

表2

图3

图4

图5

图6

图7

图8

图9

图10

图11

图12

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