Bi is one of the most fascinating catalysts for the formation of HCOO⁻ towards CO₂ electroreduction. Herein, we developed electrodeposited angular-shaped Bi microparticles (Bi MP) with exposed surfaces of {003} and {101} planes as efficient catalyst for the electroreduction of CO₂ into HCOO⁻. During CO₂ electroreduction, Bi MP achieved a Faraday efficiency (FE) for HCOO⁻ of higher than 95% over a wide range of applied potential from −0.6 to −1.1 V versus reversible hydrogen electrode (vs. RHE), whereas the FE for HCOO⁻ of Bi nanoflakes (Bi NF) with exposed surfaces of {104} and {110} planes was around 70%. At −1.1 V vs. RHE, the partial current density for HCOO⁻ of Bi MP was −271.7 mA·cm⁻², 1.56 times as high as that of Bi NF. According to kinetic analysis and mechanistic study, highly-oriented surface of Bi MP not only facilitated Faradaic process and accelerated reaction kinetics via enhancing the CO₂ activation, but also restrained competing hydrogen evolution reaction, thus boosting catalytic performance of the electroreduction of CO₂ into HCOO⁻.

All-inorganic lead-free palladium (Pd) halogen perovskites with prominent optoelectronic properties provide admirable potential for selective photo- and electroreduction of CO₂. But it remains unachieved for effectively converting the CO₂ to CO with high selectivity on Pd-based perovskites driven by solar light or electricity. Herein, high-quality Cs₂PdBr₆ microcrystals and nanocrystals were synthesized through a facile antisolvent method. Among all the reported pure-phase perovskites, the Cs₂PdBr₆ nanocrystals synthesized at 50 °C performed the highest effectiveness on CO₂ to CO conversion generating 73.8 μmol g⁻¹ of CO yield with 100% selectivity under visible light illumination (λ > 420 nm) for 3 h. Meanwhile, for the first time, we report a new application of lead-free perovskites, in which they are applied to electrocatalysis of CO₂ reduction reaction. Noticeably, they showed significant electrocatalytic activity (Faradaic yield: 78% for CO) and operation stability (10 h). And the surface reaction intermediates were dynamically monitored and precisely unraveled according to the in situ diffuse reflectance infrared Fourier transform spectra investigation. In combination with the density functional theory calculation, the reaction mechanism and pathways were revealed. This work not only provides significant strategies to enhance the photocatalytic performance of perovskites, but also shows excellent potential for their application in electrocatalysis.