<br>4d 过渡金属掺杂 g-C3N4 单分子层中电荷态和双功能 OER/ORR 电催化剂活性的理论见解,ACS Applied Materials & Interfaces

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4d 过渡金属掺杂 g-C3N4 单分子层中电荷态和双功能 OER/ORR 电催化剂活性的理论见解
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2024-01-25 , DOI: 10.1021/acsami.3c14995
Dongying Li ₁ , Aodi Zhang ₂ , Zhenzhen Feng ₂ , Wentao Wang ₁

Affiliation

探索用于双功能析氧反应（OER）和氧还原反应（ORR）的高效稳定的电催化剂对于开发可再生能源技术至关重要。然而，由于与这些双功能 OER/ORR 电催化剂相关的大量且复杂的设计空间，它们的开发提出了巨大的挑战，导致它们在实验和计算研究中成本高昂。在此，我们利用缺陷物理方法，系统地研究了4d-过渡金属（4d-TM，4d-TM = Zr、Nb、Mo、Ru、Rh、Pd 和 Ag）的形成能和双功能过电势（ _η Bi ） ) 掺杂单层超级电池 gC ₃ N ₄ (4d-TM@C ₅₄ N ₇₂ ) 基于密度泛函理论 (DFT) 计算。在富氮和富碳条件下，我们发现Rh _N @C ₅₄ N ₇₁ （Rh占据N）和Pd _N @C ₅₄ N ₇₁ （Pd占据N）的形成能小于其他4d- TM _N @C ₅₄ N ₇₁ （4d-TM 占用 N 位点）；对于4d-TM _int @C ₅₄ N ₇₂ （4d-TM 间隙位置占据），最低形成能缺陷是Pd _int @C ₅₄ N ₇₂ 。这些结果表明它们具有更好的稳定性。有趣的是，对于这些形成能较低的系统，Pd ⁰ _int @C ₅₄ N ₇₂ (η _Bi = 1.00 V) 和 Rh ¹⁺ _N @C ₅₄ N ₇₁ (η _Bi = 0。73 V）具有超低过电势，非常适合双功能 OER/ORR 电催化剂。我们发现原因是调节4d-TM@C ₅₄ N ₇₂的电荷态可以调节含氧中间体与4d-TM@C ₅₄ N ₇₂之间的相互作用强度，这在反应活性中起着至关重要的作用。此外，通过机器学习（ML）应用获得的数据表明，4d-TM和配位原子（ d _TM-OOH ）的电负性（ N _m ）和键长分别是表征OER和ORR活性的主要描述符。 4d-TM@C ₅₄ N ₇₂双功能 OER/ORR 活性的带电缺陷调节将能够优化电催化性能并开发用于可再生能源应用的潜在电催化剂。

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Theoretical Insights on the Charge State and Bifunctional OER/ORR Electrocatalyst Activity in 4d-Transition-Metal-Doped g-C3N4 Monolayers

Exploring efficient and stable electrocatalysts for the bifunctional oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is vital to developing renewable energy technologies. However, due to the substantial and intricate design space associated with these bifunctional OER/ORR electrocatalysts, their development presents a formidable challenge, resulting in their cost-prohibitive nature in both experimental and computational studies. Herein, using the defect physics method, we systematically investigate the formation energies and bifunctional overpotential (η_Bi) of 4d-transition-metal (4d-TM, 4d-TM = Zr, Nb, Mo, Ru, Rh, Pd, and Ag)-doped monolayer supercell g-C₃N₄ (4d-TM@C₅₄N₇₂) based on the density functional theory (DFT) calculations. Under N-rich and C-rich conditions, we find that the formation energies of Rh_N@C₅₄N₇₁ (Rh occupation N) and Pd_N@C₅₄N₇₁ (Pd occupation N) are smaller than that of other 4d-TM_N@C₅₄N₇₁ (4d-TM occupation N site); for the 4d-TM_int@C₅₄N₇₂ (4d-TM interstitial site occupation), the lowest-formation energy defects are Pd_int@C₅₄N₇₂. These results indicate that they have better stabilities. Interestingly, for these formation energy lower systems, Pd⁰_int@C₅₄N₇₂ (η_Bi = 1.00 V) and Rh¹⁺_N@C₅₄N₇₁ (η_Bi = 0.73 V) have ultralow overpotential and can be great candidates for bifunctional OER/ORR electrocatalysts. We find the reason is that adjusting the charge states of 4d-TM@C₅₄N₇₂ can tune the interaction strength between the oxygenated intermediates and the 4d-TM@C₅₄N₇₂, which plays a crucial role in the activity of reactions. Additionally, the data obtained through machine learning (ML) application suggest that the electronegativity (N_m) and bond length of 4d-TM and coordination atoms (d_TM-OOH) are primary descriptors characterizing the OER and ORR activities, respectively. The charged defect tuning of the bifunctional OER/ORR activity for 4d-TM@C₅₄N₇₂ would enable electrocatalytic performance optimization and the development of potential electrocatalysts for renewable energy applications.

更新日期：2024-01-25

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