Electrochemical reduction of CO2 (CO2R) to formic acid upgrades waste CO2; however, up to now, chemical and structural changes to the electrocatalyst have often led to the deterioration of performance over time. Here, we find that alloying p-block elements with differing electronegativities modulates the redox potential of active sites and stabilizes them throughout extended CO2R operation. Active Sn-Bi/SnO2 surfaces formed in situ on homogeneously alloyed Bi0.1Sn crystals stabilize the CO2R-to-formate pathway over 2400 h (100 days) of continuous operation at a current density of 100 mA cm−2. This performance is accompanied by a Faradaic efficiency of 95% and an overpotential of ~ −0.65 V. Operating experimental studies as well as computational investigations show that the stabilized active sites offer near-optimal binding energy to the key formate intermediate *OCHO. Using a cation-exchange membrane electrode assembly device, we demonstrate the stable production of concentrated HCOO– solution (3.4 molar, 15 wt%) over 100 h.
Engineering electronic properties is a promising way to design nonprecious-metal or earth-abundant catalysts toward hydrogen evolution reaction (HER). Herein, we deposited catalytically active MoS flakes onto black phosphorus (BP) nanosheets to construct the MoS-BP interfaces. In this case, electrons flew from BP to MoS in MoS-BP nanosheets because of the higher Fermi level of BP than that of MoS. MoS-BP nanosheets exhibited remarkable HER performance with an overpotential of 85 mV at 10 mA cm. Due to the electron donation from BP to MoS, the exchange current density of MoS-BP reached 0.66 mA cm, which was 22 times higher than that of MoS. In addition, both the consecutive cyclic voltammetry and potentiostatic tests revealed the outstanding electrocatalytic stability of MoS-BP nanosheets. Our finding not only provides a superior HER catalyst, but also presents a straightforward strategy to design hybrid electrocatalysts.
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