Ion transport behaviors are central to ion separation, micro-/nano-fluidics, and interfacial catalysis, yet achieving high ion transport rate and selectivity remains challenging in nonaqueous systems. Here, we propose a unique solid–liquid cooperative interface built from a layered cyano-bridged metal framework (CMF) and nonaqueous solvents to simultaneously increase cation (Li⁺) conductivity (9.5 mS·cm⁻¹) and transport selectivity (~0.9). Mechanistic analysis based on theoretical calculations, supported by electrochemical measurements, shows that the nonaqueous solvents can work as functional interfacial ligands at the surface of layered CMFs, including outer-layer solvent ligands (OSLs) and interlayer solvent ligands (ISLs), which can restructure the interfacial Li⁺ migration environment and salt speciation. It is found that OSLs with higher polarity symmetry would interact more strongly with the unsaturated metal sites on the CMF's surface, thereby promoting coordination competition at the interface, accelerating solvation-renewal dynamics, and increasing the Li⁺ transport rate. ISLs with higher polarity symmetry could stabilize a low-curvature surface of CMF, strengthen anion anchoring at the unsaturated metal sites, increase selectivity for Li⁺ transport, and further improve overall Li⁺ transport rate. Therefore, we provide a potential strategy to construct a unique solid-liquid interface using CMF solids and rationally designed interfacial solvent ligands to promote the ion transport behaviors.

The global climate crisis and the excessive consumption of fossil fuels have made photocatalytic CO₂ reduction a promising strategy for achieving carbon neutrality. However, the inherent chemical inertness of CO₂ and the rapid recombination of photogenerated charge carriers still limit its efficiency. In this study, a CeO₂/NiO composite catalyst with an octahedral orthogonal structure was synthesized by oxidation treatment using a nickel-based cyanide-bridged metal frameworks as the precursor. Characterization analyses revealed that the CeO₂/NiO composite structure significantly enhanced charge carrier separation efficiency through interfacial synergistic effects, while moderate surface lattice defects improved CO₂ adsorption and activation. Under visible light irradiation, the CO generation rate of the CeO₂/NiO reached 30.1 mmol·g⁻¹·h⁻¹, which was significantly higher than that of the original precursor, and it exhibited remarkable stability (with activity maintained at over 95% after five cycles). Mechanistic studies indicated that the optimized band structure provided sufficient thermodynamic driving force for CO₂ reduction. The interfacial electron transfer channels facilitated the directional migration of photoelectrons, while surface oxygen vacancies optimized the adsorption energy of the critical intermediate (*COOH) through localized charge redistribution.