Isomerism‐Activity Relation in Molecular Electrocatalysis: A Perspective

Abstract

This perspective provides a brief overview on the role of isomerism of secondary‐sphere functionality in molecular electrocatalysis, without which there exists a clear knowledge‐gap in defining a molecule's structure‐activity relation. The discussion unfolds how isomerism of the functionality triggers short‐range interactions in the molecule leading to unprecedented events in electrocatalysis. This perspective highlights that the isomerism of substituents makes an independent contribution to electrocatalysis over its nature and for exploiting the maximum potential of the molecule in electrocatalysis, nature of the substituent as well as its isomerism should be given consideration.

Phthalocyanine Polymer Anchored Ketjen Black Nanoparticles for Bifunctional Oxygen Electrocatalysis

“…15 In this context, the metal organic frameworks have emerged as promising candidates, with metal phthalocyanines (MPc's) being particularly noteworthy. 16,17 MPc's, inspired by bio-active N 4 macrocycles, possess a structure similar to a naturally occurring porphyrin system, 18,19 and offer structural diversity, tunable properties, high stability, and excellent redox behavior, which favors them as promising candidates for oxygen-catalytic applications when compared to metal oxides, nanoparticles, or other polymers. 20−23 Recent studies have highlighted the potential of MPc's in the design of cost-effective bifunctional electrocatalysts with enhanced efficiency for both OER and ORR.…”

“…An effective catalyst has to possess several key characteristics, such as a large surface area with dual or multiple active sites, excellent conductivity that offers many efficient pathways for mass transfer and electron conduction (because OER and ORR do not involve similar reversible reaction routes), thermal as well as chemical resistance (for long-term durability), and adherence to Sabatier’s principle when interacting with reaction intermediates (that lowers the reaction overpotential) . In this context, the metal organic frameworks have emerged as promising candidates, with metal phthalocyanines (MPc’s) being particularly noteworthy. , MPc’s, inspired by bio-active N 4 macrocycles, possess a structure similar to a naturally occurring porphyrin system, , and offer structural diversity, tunable properties, high stability, and excellent redox behavior, which favors them as promising candidates for oxygen-catalytic applications when compared to metal oxides, nanoparticles, or other polymers. − Recent studies have highlighted the potential of MPc’s in the design of cost-effective bifunctional electrocatalysts with enhanced efficiency for both OER and ORR. , For instance, Cheng et al developed an efficient bifunctional oxygen electrocatalyst by integrating iron-phthalocyanine metal–organic framework into a carbon black matrix (FePPc@CB) using a melt polymerization process . Similarly, Liao et al pyrolyzed a bimetallic FeNi–phthalocyanine-based covalent organic polymer at 800 °C (FeNi–COP-800) to obtain a bifunctional catalyst with remarkable oxygen catalytic activity .…”

Molecular fluorinated cobalt phthalocyanine immobilized on ordered mesoporous carbon as an electrochemical sensing platform for sensitive detection of hydrogen peroxide and hydrazine in alkaline medium

“…The functionalities of CoPc macrocycle are related to the electronic arrangement and electrocatalytic activity [11]. It has been well understood that electron-withdrawing substituents at the benzene rings of CoPc can activate the catalytic central Co ion toward electrochemical reactions [12,13]. Peisert [14] recently investigated the interfacial properties of CoPc and fluorinated CoPc (CoPcF16) on conductive substrate.…”

3D‐Stretched Film Ni3S2 Nanosheet/Macromolecule Anthraquinone Derivative Polymers for Electrocatalytic Overall Water Splitting

“…Carbon materials with macrocyclic frameworks, graphite and graphitelike structures have been widely studied. [2,9,10] Because of the chem ical stability, thermal stability and highly adjustable photoelectric properties, as carriers of catalyst, this kind of carbon material have been used for electrochemical applications such as OWS, oxygen evolution reaction (OER), carbon dioxide reduction, and hydrogen evolution reaction (HER). [11,12] The study also shows that the macrocyclic carbon framework material enhances the crystallization ability of ZIF 8, [13] which solves the problem of low crystallinity of metal organic frameworks prepared by traditional benzene derivatives (BZD).…”