Modulating electric field distribution by alkali cations for CO2 electroreduction in strongly acidic medium

Atomistic Understanding of Two-dimensional Electrocatalysts from First Principles

“…Besides the site engineering, modulating the local environment for reactions is another effective approach. For example, the cations in solution are known to significantly impact the CO 2 R, − and tuning them can suppress the HER and thus enable efficient CO 2 R in acidic medium . For another example, OER of magnetic electrocatalysts (e.g., NiZnFe 4 O x , CoFe 2 O 4 ) can be enhanced by external magnetic field. , Considering that some 2D electrocatalysts also have intrinsic electron spin polarization, , manipulating it by magnetic field may promote their catalytic performance as well.…”

Design strategies for markedly enhancing energy efficiency in the electrocatalytic CO2 reduction reaction

“…80,81 On the one hand, the larger cations with weak hydration, such as K + and Cs + , are more likely to adsorb on catalysts to move the potential at an outer Helmholtz plane (OHP) toward a more positive direction, consequently repulsing proton adsorption and suppressing the HER. [82][83][84] The alteration of the interfacial water structure in the electrical double layer caused by cations also has an impact on the HER. 85 On the other hand, cations would directly determine the CO 2 RR process via changing mass transport and local interaction.…”

A unifying mechanism for cation effect modulating C1 and C2 productions from CO2 electroreduction

“…However, various other experiments, where no clear activity change was observed upon (bulk) pH variations, demonstrated the possibility that the RDS involves no proton transfer 12 , 18 – 21 . Meanwhile, Chan group suggested a mechanism for the cation effect, called a field effect 16 , 17 , 22 , 23 : the electric double layer (EDL) field formed across the Helmholtz layer would stabilize the intermediates ( e.g ., *CO 2 ) via adsorbate dipole-field interaction, which can be modulated by the degree of M + accumulation at the interface 17 , 24 . Also, using the scanning electrochemical microscopic technique, the Koper group demonstrated an absence of CO 2 RR activity for CO formation without M + , which led them to propose a mechanism based on a M + -complexation (or coupling) to the CO 2 − intermediate in conjunction with their ab initio molecular dynamics (AIMD) simulation results 13 .…”