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Converting CO2 into value-added chemical fuels and functional materials by CO2 reduction reaction (CO2RR) is conducive to achieving a carbon-neutral energy cycle. However, it is still challenging to efficiently navigate CO2RR toward desirable products. Herein, we report a facile strategy to extend product species in borate-containing molten electrolyte at a positively shifted cathodic potential with a high current density (e.g. 100 mA/cm2), which can selectively electro-transform CO2 into desired products (either CO or solid carbon nanofi