Tailored p‐Orbital Delocalization by Diatomic Pt‐Ce Induced Interlayer Spacing Engineering for Highly‐Efficient Ammonia Electrosynthesis

Abstract

Electrochemical nitrate reduction to ammonia (eNO3RR) is a green and appealing method for ammonia synthesis, but is hindered by the multistep chemical reaction and competitive hydrogen generation. Herein, the synthesis of 2D SnS nanosheets with tailored interlayer spacing is reported, including both expansion and compression, through the active diatomic Pt‐Ce pairs. Taking together the experimental results, in situ Raman spectra, and DFT calculations, it is found that the compressed interlayer spacing can tune the electron density of localized p‐orbital in Sn into its delocalized states, thus enhancing the chemical affinity towards NO3− and NO2− but inhibiting hydrogen generation simultaneously. This phenomenon significantly facilitates the rate‐determining step (*NO3→*NO2) in eNO3RR, and realizes an excellent Faradaic efficiency (94.12%) and yield rate (0.3056 mmol cm−2 h−1) for NH3 at −0.5 V versus RHE. This work provides a powerful strategy for tailoring flexible interlayer spacing of 2D materials and opens a new avenue for constructing high‐performance catalysts for ammonia synthesis.

Laser-controlled tandem catalytic sites of CuNi alloys with ampere-level electrocatalytic nitrate-to-ammonia reduction activities for Zn–nitrate batteries

“…3g. 7,9,[28][29][30] Obviously, the concentration range of NO 3 À suitable for most catalysts was very narrow. In addition, the FEs of NH 3 production fluctuated dramatically, when the concentration of NO 3 À in the electrolyte slightly changed.…”

Exploring the origin of the high electro-catalytic activity for nitrate-to-ammonia conversion on electrodeposited Ni/Ru hydroxide hybrids

“…S10†). 13,20 The Ru-25CV/oNF300 also exhibits durable and high NITRR performance for up to 100 h with no apparent loss in the selectivity, as shown in Fig. S11 †…”

Highly Efficient Electroenzymatic Cascade Reduction Reaction For The Conversion of Nitrite to Ammonia

“…The volcano-like distribution of Faraday efficiency originates from the competitive hydrogen evolution reaction at more negative potentials. [37] To rule out the interference from the electrolyte itself, electrochemical experiment of the CPO-IL BMB /MWCNT-PEI bioconjugate is also conducted in the absence of NO 2 − (Figure 3a), which indicates negligible NH 4…”