Related Experiment Video
Updated: Jul 12, 2026
05:03
Precise Electrochemical Sizing of Individual Electro-Inactive Particles
Published on: August 4, 2023
Molecularity Control in Electrochemical Multi-Site Proton-Coupled Electron Transfer Reactions
1Shenzhen Grubbs Institute and Department of Chemistry, Guangming Advanced Research Institute, and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, China.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 10, 2026
Summary
Multi-site proton-coupled electron transfer (MS-PCET) enhances electrosynthesis by lowering overpotentials. This study classifies PCET reactions by molecularity, enabling new strategies for C-H activation and sustainable synthesis.
Area of Science:
- Electrochemistry
- Catalysis
- Sustainable Chemistry
Background:
- Multi-site proton-coupled electron transfer (MS-PCET) activates strong bonds efficiently.
- Electrochemical MS-PCET offers sustainability benefits but is underexploited beyond O-H and N-H bonds.
- Productive oxidative PCET often requires entropically disfavored termolecular encounters.
Purpose of the Study:
- To classify electrochemical oxidative PCET based on molecularity.
- To explore strategies for reducing molecularity in PCET reactions.
- To advance C-H bond activation and electrosynthesis through molecularity engineering.
Main Methods:
- Classification of oxidative PCET into Type I (X-H...B), Type II (X-H...Y), and Type III (Y...B) based on preassembled pairs.
- Analysis of reaction feasibility based on bond dissociation free energy (BDFE) gaps.
- Review of advances in electrochemical N-H/O-H activation, M-H generation, and C-H PCET.
Main Results:
- Reducing molecularity via preorganization opens concerted reaction channels.
- Feasibility of PCET is governed by the BDFE gap between donor/acceptor pairs and the target X-H bond.
- Demonstrated advances in various electrochemical PCET applications, including emerging C-H activation.
Conclusions:
- Molecularity engineering is key to unlocking efficient electrochemical PCET.
- This approach facilitates sustainable electrosynthesis, particularly for challenging C-H bond activation.
- Prospects include asymmetric catalyst design and metal hydride interfacial PCET.
More Related Videos
Related Concept Videos
01:30Processes at Electrodes
The electrode interacts with ions in the electrolyte solution at its interface. The rate of oxidation and reduction depends on the speed at which electrons can transfer through this interface. As ions attach to or leave the electrode surface, the electrode acquires a charge, and an electrical potential forms across the interface, making the process more difficult to reach equilibrium. The charge on the electrode affects the local ion concentrations in the solution, though thermal motion...
01:17Controlled-Potential Coulometry: Electrolytic Methods
Controlled-potential coulometry, also known as potentiostatic coulometry, employs a three-electrode system in which the working electrode's potential is precisely regulated using a potentiostat. Platinum working electrodes are utilized for positive potentials, while mercury pool electrodes are favored for extremely negative potentials. The platinum counter electrode is separated from the analyte using a membrane or salt bridge to avoid interference in the analysis.
The chosen potential ensures...
The chosen potential ensures...
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
01:26Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
01:32Chemiosmosis
Oxidative phosphorylation is a highly efficient process that generates large amounts of adenosine triphosphate (ATP), the basic unit of energy that drives many cellular processes. Oxidative phosphorylation involves two processes— the electron transport chain and chemiosmosis.
Electron Transport Chain
The electron transport chain involves a series of protein complexes on the inner mitochondrial membrane that undergo a series of redox reactions. At the end of this chain, the electrons reduce...
Electron Transport Chain
The electron transport chain involves a series of protein complexes on the inner mitochondrial membrane that undergo a series of redox reactions. At the end of this chain, the electrons reduce...
01:29Electron Transport Chain Components
The electron transport chain (ETC) is a crucial metabolic pathway that facilitates energy conversion in prokaryotic and eukaryotic cells. In eukaryotes, the ETC comprises four membrane-associated protein complexes in the inner mitochondrial membrane. In prokaryotes, the ETC in the plasma membrane can vary in composition, with fewer or different complexes depending on the organism and environmental conditions. These complexes transfer electrons from electron donors, such as NADH and FADH2, to...