Understanding hydrogen electrocatalysis by probing the hydrogen-bond network of water at the electrified Pt–solution interface

Molecular Insights into the Stability of Titanium in Electrolytes Containing Chlorine and Fluorine Ions

“…The DDA (double donor and single acceptor of protons for central water) configuration hydrogen bond (HB) exhibits the strongest ability to promote electron loss . The experiments combining electrochemistry and in situ spectroscopy also support the redirection of HB networks by interface electric field (IEF), as well as the directional migration of protons and hydroxide ions in the electrode interface double layer . It is inferred that the reconstruction of HB networks exhibits a blocking effect in the electrode HER/HOR reactions involving protons.…”

“…25 The experiments combining electrochemistry and in situ spectroscopy also support the redirection of HB networks by interface electric field (IEF), as well as the directional migration of protons and hydroxide ions in the electrode interface double layer. 26 It is inferred that the reconstruction of HB networks exhibits a blocking effect in the electrode HER/HOR reactions involving protons. However, the structural configuration of HB networks in different corrosive environments is not yet clearly understood, and whether HB networks play a role in the metal corrosion reaction itself is still a mystery.…”

Electric Double Layer Effects in Electrocatalysis: Insights from Ab Initio Simulation and Hierarchical Continuum Modeling

“…76 The importance of interfacial hydrogen-bonding networks for reaction kinetics has been continuously emphasized very recently, which is greatly advancing the fundamental understanding of modern electrocatalysis. 145,146 Apart from the simple hydrogen electrocatalytic reactions, the ab initio simulation is also gradually being applied to study the complex multielectron multiproton transfer reactions (such as the ORR/OER, CO 2 RR, and CO reduction), mainly focusing on determining the entire reaction pathway at the electrochemical interface, obtaining the energetics along the reaction process, and determining the key interfacial EDL factors that affect the reaction performance. 147−151 In this regard, the main challenge is that the multielectron multiproton transfer reaction not only involves more elementary steps but also has many possible products and corresponding reaction mechanisms.…”

Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces

“…28−31 Recently, significant improvement of ORR kinetics on Pt and Au electrocatalysts has been demonstrated through tuning proton transfer by modifying electrodes with protonic ionic liquids, while ORR reaction pathways on a heterogenized molecular Cu electrocatalyst can be controlled through a lipidbound proton carrier. 16,19 Progress has been made in understanding the critical role of protons in the electrochemical transformation of organic molecules (formic acid, 32 alcohol, 33 nitrobenzene 34 ) and hydrogen 35,36 at heterogeneous interfaces. Molecular control of heterogeneous electrocatalysis has been achieved through the graphite-conjugated acid approach.…”

“…Proton transfer plays a critical role in diverse chemical, biochemical, and electrochemical processes. − The hydrogenase enzyme, microalgae, and bacteria achieve reversible proton-coupled chemical transformations by precisely controlling proton movement to and from the active sites of, for example, iron or nickel complexes with organic ligands (e.g., porphyrins or polypyridine). − To mimic the function of how natural systems manipulate proton transfer, many artificial molecular electrocatalysts have been designed and synthesized in which certain basic pendant groups function as proton relays to promote proton transfer and improve reaction kinetics. − Recently, significant improvement of ORR kinetics on Pt and Au electrocatalysts has been demonstrated through tuning proton transfer by modifying electrodes with protonic ionic liquids, while ORR reaction pathways on a heterogenized molecular Cu electrocatalyst can be controlled through a lipid-bound proton carrier. , Progress has been made in understanding the critical role of protons in the electrochemical transformation of organic molecules (formic acid, alcohol, nitrobenzene) and hydrogen , at heterogeneous interfaces. Molecular control of heterogeneous electrocatalysis has been achieved through the graphite-conjugated acid approach. , Progress has also been made in understanding how noncovalent interactions affect heterogeneous electrocatalysis through tuning electrolyte composition. − We, therefore, hypothesize that a proton relay can be built in heterogeneous electrocatalysts to more efficiently promote proton transfer and improve electrochemical reaction kinetics for which a proton is involved in the elementary step of the specific reaction (i.e., H + -containing reactions)Scheme .…”