A Density Functional Theory Study of Electrochemical Nitrogen Reduction to Ammonia on the (100) Surface of Transition-Metal Oxynitrides
A Density Functional Theory Study of Electrochemical Nitrogen Reduction to Ammonia on the (100) Surface of Transition-Metal Oxynitrides
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DOI：
10.1021/acs.jpcc.2c04119
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发表时间：
2022-09
期刊：
影响因子：
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通讯作者：
Damilola Ologunagba;Shyam Kattel
中科院分区：
文献类型：
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作者：
Damilola Ologunagba;Shyam Kattel
与能源和碳密集型的工业化Haber-Bosch工艺相比，在环境条件下电化学氮（N2）还原反应（ENRR）生产氨（NH3）具有吸引力。然而，需要有效的催化剂来打破n2分子中的N≡N键，将其转化为NH3。过渡金属氮氧化物（TMNOs）在低电位下具有良好的ENRR活性。本文通过密度泛函理论（DFT）计算，研究了TM = Co、Cr、Cu、Fe、Hf、Mn、Nb、Ni、Sc、Ta、Ti、V、Y、Zn和Zr的TMNO（100）表面的ENRR活性。我们的DFT计算和微动力学建模结果表明，ENRR在MnNO、CrNO、FeNO、CuNO、HfNO和VNO的（100）表面以低施加电位进行。此外，我们的计算揭示了ENRR中间体的极限势和结合能之间存在类似火山的关系，确定了氮结合能和N2H结合能是ENRR在TMNO（100）表面活性的描述符。
The electrochemical nitrogen (N2) reduction reaction (ENRR) to produce ammonia (NH3) under ambient conditions is attractive compared to the energy- and carbon-intensive industrialized Haber–Bosch process. However, efficient catalysts are needed to break an N≡N bond in an N2molecule to convert it to NH3. Transition-metal oxynitrides (TMNOs) have shown promising ENRR activities at low potentials. Here, density functional theory (DFT) calculations are performed to study the ENRR activity of TMNO(100) surfaces for TM = Co, Cr, Cu, Fe, Hf, Mn, Nb, Ni, Sc, Ta, Ti, V, Y, Zn, and Zr. Our DFT calculations and microkinetic modeling results show that the ENRR proceeds at a low applied potential on the (100) surfaces of MnNO, CrNO, FeNO, CuNO, HfNO, and VNO. Furthermore, our calculations reveal a volcano-like relation between the limiting potential and binding energy of ENRR intermediates identifying nitrogen binding energy and N2H binding energy as descriptors for ENRR activity on TMNO(100) surfaces.