Catalyst
supports play an essential role in catalytic reactions,
hinting at pronounced metal–support effects. Zeolites are a
propitious support in heterogeneous catalysts, while their use in
the electrocatalytic CO2 reduction reaction has been limited
as yet because of their electrically insulating nature and serious
competing hydrogen evolution reaction (HER). Enlightened by theoretical
prediction, herein, we implant zinc ions into the structural skeleton
of a zeolite Y to strategically tailor a favorable electrocatalytic
platform with remarkably enhanced electronic conduction and strong
HER inhibition capability, which incorporates ultrafine cadmium oxide
nanoclusters as guest species into the supercages of the tailored
12-ring window framework. The metal d-bandwidth tuning of cadmium
by skeletal zinc steers the extent of substrate–molecule orbital
mixing, enhancing the stabilization of the key intermediate *COOH
while weakening the CO poisoning effect. Furthermore, the strong cadmium–zinc
interplay causes a considerable thermodynamic barrier for water dissociation
in the conversion of H+ to *H, potently suppressing the
competing HER. Therefore, we achieve an industrial-level partial current
density of 335 mA cm–2 and remarkable Faradaic efficiency
of 97.1% for CO production and stably maintain Faradaic efficiency
above 90% at the industrially relevant current density for over 120
h. This work provides a proof of concept of tailored conductive zeolite
as a favorable electrocatalytic support for industrial-level CO2 electrolysis and will significantly enhance the adaptability
of conductive zeolite-based electrocatalysts in a variety of electrocatalysis
and energy conversion applications.