Dual Interface-Engineered Tin Heterostructure for Enhanced Ambient Ammonia Electrosynthesis

Abstract

Electrocatalytic nitrogen reduction reaction (NRR) represents a promising alternative route for sustainable ammonia synthesis, which currently dominantly relies on the energyintensive Haber−Bosch process, while it is significantly hampered by the sluggish reaction kinetics due to the short of glorious electrocatalysts. In this work, we report an efficient porous tin heterostructure with intimate dual interfaces for electrosynthesis of ammonia, which exhibits outstanding NRR efficiency with an NH 3 yield rate and Faradaic efficiency as high as 30.3 μg h −1 mg −1 cat and 41.3%, respectively, and excellent stability as well at a low potential of −0.05 V (vs RHE) in 0.1 M Na 2 SO 4 solution under ambient conditions. This matrix value is superior to the analogue Sn-based heterostructures with a single interface and outperforms the currently state-of-the-art Sn-based catalysts. Comprehensive characterizations and theoretical calculations uncovered the formation of the unique intimate dual interfaces in the tin heterostructure promoting the enhancement of the NRR process, which not only effectively exposes more active sites for stronger N 2 chemisorption and activation but also accelerates the interfacial electron transfer and reduces the free energy barrier for the rate-determining *N 2 H formation step, highlighting the importance of the dual interface effect for the design of electrocatalysts in catalysis.

Progress of Experimental and Computational Catalyst Design for Electrochemical Nitrogen Fixation

“…∼−0.40 150 NiSb, 148 NiPc, 149 NiO@TiO 2 , 150 Ni-BCN 151 10. 75 129,162,164,165 ∼30 161 −0.05 165 ∼−0.80 166 Rh/GDY, 129 Y-TiO 2 -C, 161 BP@SnO 2−x , 162 Te-C, 163 Ag/TiO 2 , 164 SnO 2 /NC, 165 Sn/SnS 2 , 166 SnS 2 @Ni, 167 Y 1 /NC, 168 C@YSZ, 169 Te/SeO 170 Iso-eSi x , 178 F/PC, 179 Cl-GDY, 180 CNS 181 h-BNNS, 182 PNG, 183 LiN 2 /Mo, 31 LiNR, 37 Li-SICON, 38 LiCl, 39 HBTCu 40 150−200 atm are applied to ensure the favorable reaction equilibrium toward the NH 3 products. Thus, high temperature and pressure are needed to guarantee a significant turnover frequency (TOF, Figure 2B).…”

A General Strategy toward Metal Sulfide Nanoparticles Confined in a Sulfur‐Doped Ti3C2Tx MXene 3D Porous Aerogel for Efficient Ambient N2 Electroreduction

“…Such interaction can stabilize the CoS NPs and favor the charge/electron transport in-between. [55,56] Two distinct peaks at 162.6 and 163.8 eV are attributable to S 2p 3/2 and 2p 1/2 of the S 2− species in CoS [57] in the S 2p spectrum, respectively (Figure 2d). In addition, the presence of the peak at 161.5 eV, assignable to the C-Ti-S bond, [58] indicates the incorporation of S in the MXene framework associated with the formation of S-Ti bond.…”

Mn-Doped Bi2O3 Nanosheets from a Deep Eutectic Solvent toward Enhanced Electrocatalytic N2 Reduction

“…NH 3 synthesis based on the electrochemical nitrogen reduction reaction (NRR) has recently been considered as a valuable strategy, which can be operated under ambient conditions without disastrous pollution. − However, the electrochemical NRR is severely restricted by the sluggish reaction kinetics of breaking the ultrastable NN bond and the competitive HER, resulting in a poor NH 3 yield rate and low faradaic efficiency (FE). , Consequently, it is extremely urgent to design advanced catalysts for achieving admirable NRR performance. Until now, a diversity of metallic and nonmetallic catalysts have been considered to be promising candidates toward the electrochemical NRR. − Among others, Bi-based materials are attractive catalysts for the electrochemical NRR. Particularly, Bi-based catalysts are conducive to adsorbing and activating N 2 owing to the strong interaction between Bi 6p orbitals and N 2p orbitals, which can effectively suppress the competitive HER. − As a typical Bi-based catalyst, Bi 2 O 3 demonstrates promising electroactivity for the NRR, , but the large overpotential leads to an unsatisfactory FE.…”