A novel Pb/C interlayer is introduced on Na ₃ Zr ₂ Si ₂ PO ₁₂ solid electrolyte, which offers perfect Na wettability, negates interfacial resistance, and allows in situ fabrication of “Na-less” anodes for stable solid-state Na-metal batteries.

The implementation of low-cost transition-metal complexes in CO₂ reduction reaction (CO₂RR) is hampered by poor mechanistic understanding. Herein, a carbon-supported copper bis-(terpyridine) complex enabling facile kilogram-scale production of the catalyst is developed. We directly observe an intriguing baton-relay-like mechanism of active sites transfer by employing a widely accessible operando Raman/Fourier-transform infrared spectroscopy analysis coupled with density functional theory computations. Our analyses reveal that the first protonation step involves Cu-N bond breakage before the *COOH intermediate forms exclusively at the central N site, followed by an N-to-Cu active site transfer. This unique active site transfer features energetically favorable *CO formation on Cu sites, low-barrier CO desorption and reversible catalyst regeneration, endowing the catalyst with a CO selectively of 99.5 %, 80 h stability, and a turn-over efficiency of 9.4 s⁻¹ at −0.6 V vs. the reversible hydrogen electrode in an H-type cell configuration. We expect that the approach and findings presented here may accelerate future mechanistic studies of next-generation CO₂RR electrocatalysts.

Selective photocatalytic conversion of CO₂ into liquid fuels via single component metal oxides represents an attractive strategy to achieve carbon balance and mitigate global warming. Herein, we for the first time propose that the integration of porous channel confinement and oxygen vacancy (V_O) for synergistically regulating the generation of key intermediates, enables highly selective CO₂ reduction and the controllable switches of specific CH₃OH or CO reaction pathways. In situ photoelectric characterization and theoretical calculations ensure that the versatile porous structure endows ultrathin CuO with an enrichment of catalytic sites coverage, improved adsorption microenvironment, and a short charge transport distance, assuring the excellent mass-transport and binding capability of reactants. This helps to facilitate inert CO₂ into a key reactive intermediate. Furthermore, the V_O near the porous interface, which is an actual catalytic site can regulate the formation energy of key intermediates for CO₂ activation, so that the adsorbed *CO can selectively generate a thermodynamically favorable *CHO intermediate with the corresponding Gibbs free energy change value being −0.09 eV (vs. 1.86 eV of perfect CuO), thus triggering a distinctive CH₃OH reaction pathway, rather than desorption, to release CO. Benefiting from these merits, the optimal CuO with a precise design enables the effective CO₂ photoreduction into value-added CH₃OH at an evolution rate of 12.3 μmol g⁻¹ h⁻¹, a selectivity of 62.5%, and more importantly, a robust durability is realized, which is superior to most of the previously reported photocatalysts until now. This work sheds light on the fact that defect-enrichment in a porous interface can customize the unique reaction pathway for the CO₂ photoreduction to liquid fuels and offers a novel insight for the design of cheap and effective CO₂ photocatalysts.

A dendrite-suppressed, utilization-improved metallic Li anode was fabricated via a record-fast (1.0 s) infusion of molten Li into Pb-decorated carbon cloth at 250 °C.