Pre‐Adsorbed H‐Assisted N₂ Activation on Single‐Atom Cadmium‐O₅ Decorated In₂O₃ for Efficient NH₃ Electrosynthesis

Abstract

The electrocatalytic nitrogen reduction reaction (NRR) provides a promising avenue for sustainable and decentralized green ammonia (NH3) synthesis. To promote the NRR, the design and synthesis of efficient electrocatalysts with an elucidated reaction mechanism is critically important. Here, surface hydrogenation‐facilitated NRR is demonstrated to yield NH3 at low overpotentials on oxygen‐deficient In2O3 plates decorated with single atom CdO5 that have a weak N2‐binding capability. Adsorbed *H is calculated to be first produced via the Volmer reaction (H2O + e− → *H + OH−) and then reacts with dissolved N2 to generate *N2H2, which is likely the rate determining step (RDS) of the whole process. Cd atoms and oxygen vacancies in In2O3 jointly enhance the activation of N2 and accelerate the RDS, boosting the NRR. An NH3 production rate of as high as 57.5 µg h−1 mgcat−1 is attained at a mild potential, which is retained to a large extent even after 44 h of continuous polarization.

Electronic Perturbation of Isolated Fe Coordination Structure for Enhanced Nitrogen Fixation

“…Additionally, the yield of hydrazine byproduct in the reaction system promoted by FeN 2 B 2 –C is negligible, which indicates excellent selectivity toward NRR (Figure S26). The excellent NH 3 yield of FeN 2 B 2 –C surpasses the performance of numerous recently reported electrocatalysts for aqueous NRRs (Figure i). ,− …”

Carbon black supported manganese phthalocyanine: Efficient electrocatalyst for nitrogen reduction to ammonia

“…A high (10.82 eV) energy band gap exists between the lowest unoccupied molecular Initially, the σ (2p) of N 2 shares its electron with the vacant d orbital of Mn and then returns to the anti-bonding (π*2p) orbital of nitrogen that breaks the bond order (Scheme 1B). 72 The cloud of π-electron present in carbon black is key reason for the assembly of MnPc by π-π stacking interactions (Scheme 1C), which gives a path to transfer an electron from an electron donor to an acceptor, which further helps nitrogen reduction. Scheme 1D shows a probable mechanism for N 2 to NH 3 conversion where nitrogen is first adsorbed on the catalytic surface, which is further activated by applying a reduction potential.…”

Recent Developments of Dual Single‐Atom Catalysts for Nitrogen Reduction Reaction

“…Ru@ZrO 2 /NC [22] 3.7 mgh À 1 mg Ru À 1 ~21 % OÀ V 2 À NC [14] 26.1 μg h À 1 mg À 1 77.2 % VPC-NC 12.5 μg h À 1 mg À 1 ~70 % PdPb/C [23] 37.68 μg mg À 1 cat h À 1 , 7.54 μg cm À 2 h À 1 5.79 % Pd/C 4.8 μg mg À 1 cat h À 1 0.15 % Fe, MoÀ N/C [24] 1.52×10 À 6 mol h Fe, Pt, Ni, FeNi [26] 1.33×10 À 12 À 3.80×10 À 12 mol/kg 1.1-41 % Cd/In 2 O 3 (V O ) [27] 57.5 μg h À 1 mg cat…”