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Antimony (Sb) as a low-toxic and cost-effective metal is a promising material to catalyse CO 2 electroreduction to formate with practical viability. However, monometallic Sb suffers from intrinsically low catalytic activity and the competing hydrogen evolution. Here, we report nanoporous Sb-Bi alloys for substantially improving the catalytic activity of Sb and suppressing hydrogen evolution. The optimal Sb-Bi alloy exhibits a maximum Faradaic efficiency of 95.8 % toward formate production, surpassing the 11.6 % of monometallic Sb counterpart. Operating the catalyst in the flow cell demonstrates a formate partial current density of 734 mA cm−2 and cathodic energy efficiency of 59 % at a moderate overpotential of 800 mV, representing a record formate-production performance so far. Experimental and theoretical studies indicate that the Sb-Bi interactions activate Sb sites to selectively stabilize *OCHO intermediates, facilitating CO 2 -to-formate conversion. This work offers insights in manipulating bimetallic interactions to transform inert materials into active catalysts for efficient electrocatalysis. [Display omitted] • Sb-Bi interactions induce electrocatalytic switching from HER to CO 2 ER. • Sb 2 Bi 6 exhibits a maximum formate selectivity of 95.8 % in an H-type cell. • Sb 2 Bi 6 achieves a record formate activity of 734 mA cm−2 in a flow cell. • Sb-Bi interactions facilitate Sb sites to stabilize *OCHO for formate formation. [ABSTRACT FROM AUTHOR]

Alloying Ni with Pd lowers the overpotential of benzaldehyde hydrogenation and obtains a reaction rate 20 times higher than that of Ni at 0.1 V vs. RHE, which is ascribed to the lower binding energy of benzaldehyde on the metal surface revealed by the in-situ IR study. [Display omitted] • Nanoporous nanowire NiPd alloys were synthesized using a dealloying method. • Alloying Ni and Pd lowers the overpotential of ECH of benzaldehyde. • The activity of NiPd alloy is comparable with Pd. • In-situ IR study reveals that Pd tunes the binding strength of adsorbed benzaldehyde. Ni is one of the most promising catalysts in aldehydes hydrogenation, although the high overpotential and low Faradaic efficiency limit its electrocatalytic performances. Here we introduce an effective and facile alloying strategy to tune the electronic structure of Ni. We demonstrate that alloying Pd to Ni can significantly boost the electrocatalytic performances of benzaldehyde hydrogenation and lower the overpotential to the level of pure Pd. Pd introduction enhances the electrocatalytic hydrogenation process over hydrogen evolution reaction (HER), and results in an increased Faradaic efficiency. The npnw-Ni 82 Pd 18 catalyst shows the optimal atomic ratio of Ni and Pd among the explored catalysts, and achieved a turnover frequency (TOF) value of 1387 mol mol metal -1h-1 at -0.1 V vs. reversible hydrogen electrode (RHE), higher than that of npnw-Ni (60 mol mol metal -1h-1) and comparable to np-Pd (1306 mol mol metal -1h-1) under the same reaction conditions. In-situ surface-enhanced infrared absorption spectroscopy study reveals that the electronic interactions between Ni and Pd would activate the adsorbed benzaldehyde, and therefore result in an enhanced activity in benzaldehyde hydrogenation. [ABSTRACT FROM AUTHOR]