新兴高性能三功能ORR/OER/HER单原子催化剂的理论预测：锚定到π-π共轭石墨碳氮化物（g-C10N3）中的过渡金属,Physical Chemistry Chemical Physics

当前位置： X-MOL 学术 › Phys. Chem. Chem. Phys. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

新兴高性能三功能ORR/OER/HER单原子催化剂的理论预测：锚定到π-π共轭石墨碳氮化物（g-C10N3）中的过渡金属
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2023-11-17 , DOI: 10.1039/d3cp04142e
Haiye Zhu ₁ , Yingjie Feng ₂ , Desheng Zheng ₃ , Xiuyun Zhao ₄ , Yue Zhou ₂ , Xiaoyue Fu ₂ , Lei Zhao ₁ , Xin Chen ₁

Affiliation

高性能三功能氧还原/析氧/析氢反应（ORR/OER/HER）电催化剂的设计已成为当前的研究热点。在这项工作中，我们报道了一系列由九种过渡金属（Fe、Co、Ni、Ru、Rh、Pd、Os、Ir 和 Pt）形成的单原子催化剂，锚定在 gC 10 _N 3_上（即 TM@通过密度泛函理论方法， gC ₁₀ N ₃）作为有前途的三功能电催化剂来替代贵金属催化剂。所有TM@gC ₁₀ N ₃均具有良好的热力学和电化学稳定性。特别是，Rh@gC ₁₀ N ₃和Ir@gC ₁₀ N ₃表现出极低的ORR/OER过电势，分别为0.26/0.28 V和0.34/0.41 V。此外，它们的氢吸附自由能值接近Pt(111)，分别为0.16和-0.16 eV。计算结果表明Rh@gC ₁₀ N ₃和Ir@gC ₁₀ N ₃有很大概率成为三功能电催化剂。_{通过对Rh@gC 10} N ₃动力学机制的分析可以得出，四电子ORR途径更有利于在Rh@gC ₁₀ N ₃上发生，因为形成该途径的能垒较低。^{此外，*OH + H +} + e ⁻ → * + H ₂ O步骤在动力学中具有最高的能垒，这与该步骤是热力学中潜在的决定步骤是一致的。_{最终，所考虑的溶剂化效应对筛选后的Rh@gC 10} N ₃和Ir@gC ₁₀ N ₃的催化性能影响不大，即使在500 K的高温下，这两种催化剂的结构也没有明显的畸变。 2 ps 模拟。我们的计算将为此类催化剂的未来实验合成和设计提供明确的指导。

"点击查看英文标题和摘要"

Theoretical prediction of emerging high-performance trifunctional ORR/OER/HER single-atom catalysts: transition metals anchored into π–π conjugated graphitic carbon nitride (g-C10N3)

The design of high-performance trifunctional oxygen reduction/oxygen evolution/hydrogen evolution reactions (ORR/OER/HER) electrocatalysts has become the current research focus. In this work, we report a series of single-atom catalysts formed by nine kinds of transition metal (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt) anchored in g-C₁₀N₃ (namely TM@g-C₁₀N₃) as promising trifunctional electrocatalysts to replace precious metal catalysts by density functional theory methods. All TM@g-C₁₀N₃ have good thermodynamic and electrochemical stability. Especially, Rh@g-C₁₀N₃ and Ir@g-C₁₀N₃ exhibit extremely low ORR/OER overpotentials with the values of 0.26/0.28 V and 0.34/0.41 V, respectively. Besides, their hydrogen adsorption free energy values are close to Pt(111), with their values being 0.16 and −0.16 eV, respectively. The calculated results indicate that Rh@g-C₁₀N₃ and Ir@g-C₁₀N₃ can become trifunctional electrocatalysts with great probability. Through the analysis of the dynamic mechanism for Rh@g-C₁₀N₃, it can be concluded that the four-electron ORR pathway is more conducive to occurring on Rh@g-C₁₀N₃ because the energy barrier forming this pathway is lower. Besides, the step of *OH + H⁺ + e⁻ → * + H₂O has the highest energy barrier in dynamics, which is consistent with this step being a potential determining step in thermodynamics. Ultimately, the solvation effect considered has little effect on the catalytic performance of screened Rh@g-C₁₀N₃ and Ir@g-C₁₀N₃, and even at a high temperature of 500 K, the structures of these two catalysts have no significant distortion after 2 ps simulations. Our calculations will provide clear guidance for future experimental synthesis and design of such catalysts.

更新日期：2023-11-17

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南