Mastering the Electrified Interface Microenvironment for Selective Electrocatalysis

Area of Science:

• Electrocatalysis for sustainable energy conversion and chemical synthesis.
• Interfacial engineering for optimizing reaction selectivity and kinetics.

Background:

• Practical electrocatalysis is limited by side reactions and mass transport at electrode-electrolyte interfaces.
• Conventional methods focus on catalyst optimization, often neglecting the crucial role of the interfacial microenvironment.
• Electrolyte composition significantly impacts interfacial properties like proton reactivity and ion distribution.

Purpose of the Study:

• To advocate for integrated electrocatalyst design and interfacial microenvironment engineering.
• To demonstrate how electrolyte components can dynamically regulate the interface for improved electrocatalytic performance.
• To provide a mechanism-driven framework for designing next-generation electrochemical systems.

Main Methods:

• Operando characterization techniques (in situ spectroscopy, electrochemical impedance).
• Multiscale simulation methods (density functional theory, ab initio molecular dynamics).
• Systematic case studies using various electrolyte components (cations, anions, cosolvents, polymers).

Main Results:

• Effective microenvironment control spans short-range (ion-solvent interactions) and long-range (interfacial gradients) effects.
• Electrolyte components can reshape the interface, influencing proton-coupled electron transfer (PCET) pathways.
• Matched catalyst-electrolyte pairs enable selective promotion of desired reactions and suppression of competing pathways.

Conclusions:

• Mastering the interfacial microenvironment is as critical as catalyst design for efficient electrocatalysis.
• Integrated strategies combining catalyst and electrolyte engineering are essential for advancing sustainable energy solutions.
• This work promotes a mechanism-driven approach for developing advanced electrochemical systems.