Heterogeneous electrocatalytic reduction of CO₂ promoted by secondary coordination sphere effects

Abstract

The incorporation of secondary coordination sphere effects to rationally modulate electrochemical CO2 reduction on heterogeneous catalysts is reviewed.

Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

“…Finally, the reaction environment within MOFs and related systems can be tuned to impart secondary coordination sphere effects in an enzyme-inspired fashion. 21 This has recently been exemplied through the graing of pyridine units that stabilize the CO 2 c À intermediate on a Co-protoporphyrin active site en route to the reduction of CO 2 to CO in a metal-organic layer. 22 One strategy recently established in the MOF community is the use of organic linkers that are missing functional groups that bind to the metal nodes.…”

Operando spectroscopy of nanoscopic metal/covalent organic framework electrocatalysts

“…Finally, the pockets within the MOF/ COF framework can be functionalized to act in an enzymemimetic manner through secondary coordination sphere effects. 22,23 Here, the catalytic pockets stabilize intermediates, minimize reorganization energies and thermodynamically and/or kinetically direct the reaction to efficiently proceed solely through the desired pathway.…”

Understanding the Local Chemical Environment of Bioelectrocatalysis

“…The local CO2RR environment has been extensively modelled and conclusions applied to improve the selectivity of heterogeneous, [21][22][23][24][25] and heterogenised molecular catalysts. [26][27][28][29] Due to competition between HER and CO2RR when using synthetic catalysts, compromises, such as basicity, are often made to minimise the HER even at the cost of CO2RR activity due to the overall benefit of selectivity.…”