Regulating intermediate adsorption and H2O dissociation on a diatomic catalyst to promote electrocatalytic nitrate reduction to ammonia,Energy & Environmental Science

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Regulating intermediate adsorption and H2O dissociation on a diatomic catalyst to promote electrocatalytic nitrate reduction to ammonia
Energy & Environmental Science ( IF 32.4 ) Pub Date : 2024-08-07 , DOI: 10.1039/d4ee02747g
Xiaoxue Zhang _{1,

2} , Xiaokang Liu _{1,

2} , Zhen-Feng Huang _{1,

2,

3} , Li Gan _{1,

2} , Shishi Zhang _{1,

2} , Ru Jia _{1,

2} , Muhammad Ajmal _{1,

2} , Lun Pan _{1,

2,

3} , Chengxiang Shi _{1,

2,

3} , Xiangwen Zhang _{1,

2,

3} , Guidong Yang ₄ , Ji-Jun Zou _{1,

2,

3}

Affiliation

Electrochemical conversion of nitrate (NO₃⁻) is an efficient approach to reduce NO₃⁻ pollutants and it offers a promising alternative for sustainable NH₃ synthesis. However, this process is limited by the mismatched reaction kinetics of NO₃⁻ discharge, active hydrogen (H*) formation via water dissociation, and stepwise hydrogenation processes. Herein, using density functional theory (DFT) calculations, we screened a library of Cu–M diatomic catalysts coordinated with a N doped carbon matrix (Cu–M–N–C, M = Fe, Co, Ni, Mn, Zn) by balancing N-containing intermediate adsorption and H₂O dissociation barriers. Among these catalysts, Cu–Fe–N–C demonstrates the best performance with a NH₃ yield rate of 1.22 mmol h⁻¹ cm⁻² and a high Faradaic efficiency (FE) for NH₃ synthesis of 95.08% at −0.8 V vs. the reversible hydrogen electrode, in which diatomic sites facilitate the first NO₃⁻ discharge step to generate adsorbed *NO₃ and lower the energy barriers of the following hydrogenation/dehydration steps. More importantly, the incorporated Fe sites could promote the H₂O dissociation, providing a large supply of H* for the deep hydrogenation of N-containing intermediates. This work reveals the tunable bonding interactions of diatomic sites with multiple reactant/intermediates, offering a new avenue for rational design of highly efficient atomic-level dispersed catalysts for both NO₃⁻ abatement and NH₃ synthesis.

中文翻译：

调节双原子催化剂上的中间吸附和H2O解离促进电催化硝酸盐还原为氨

硝酸盐（NO ₃ ^- ）的电化学转化是减少NO ₃ ^-污染物的有效方法，并且为可持续NH ₃合成提供了一种有前景的替代方案。然而，该过程受到NO ₃ ^-放电、通过水离解形成活性氢(H*) 以及逐步氢化过程的不匹配反应动力学的限制。在此，利用密度泛函理论（DFT）计算，我们筛选了与氮掺杂碳基体（Cu-M-N-C，M = Fe，Co，Ni，Mn，Zn）配位的Cu-M双原子催化剂库：平衡含氮中间吸附和H ₂ O解离势垒。在这些催化剂中，Cu-Fe-N-C表现出最好的性能，NH ₃产率为1.22 mmol h ^-1 cm ^-2 ，NH ₃合成的法拉第效率（FE）在-0.8 V vs 95.08%可逆氢电极，其中双原子位点促进第一个NO ₃ ^-放电步骤产生吸附的*NO ₃并降低后续氢化/脱水步骤的能垒。更重要的是，掺入的Fe位点可以促进H ₂ O解离，为含氮中间体的深度氢化提供大量的H*。这项工作揭示了双原子位点与多种反应物/中间体的可调节键合相互作用，为合理设计用于NO ₃ ⁻减排和NH ₃合成的高效原子级分散催化剂提供了新途径。

更新日期：2024-08-07

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