Nano Research ( IF 9.5 ) Pub Date : 2023-09-08 , DOI: 10.1007/s12274-023-6057-4
Chunyao Fang , Xian Wang , Qiang Zhang , Xihang Zhang , Chenglong Shi , Jingcheng Xu , Mengyu Yang
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Emerging as a prominent area of focus in energy conversion and storage technologies, the development of highly active metal-based single-atom catalysts (SACs) holds great significance in searching alternatives to replace precious metals toward the efficient, stable, and low-cost hydrogen evolution reaction (HER), as well as the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). Combining the tremendous tunability of ligand and coordination environment with rich metal-based electrocatalysts can create breakthrough opportunities for achieving both high stability and activity. Herein, we propose a novel and stable holey graphene-like carbon nitride monolayer g-C16N5 (N4@g-C16N3) stoichiometries interestingly behaving as a natural substrate for constructing SACs ((TM-N4)@g-C16N3), whose evenly distributed holes map rich and uniform nitrogen coordination positions with electron-rich lone pairs for anchoring transition metal (TM) atoms. Then, we employed density functional theory (DFT) calculations to systematically investigate the electrocatalytic activity of (TM-N4)@g-C16N3 toward HER/OER/ORR, meanwhile considering the synergistic modulation of H-loading and O-coordination ((TM-NxO4−x)@g-C16N3-H3, x = 0–4). Together a “four-step procedure” screening mechanism with the first-principles high-throughput calculations, we find that (Rh-N4) and (Ir-N2O2-II) distributed on g-C16N3-H3 can modulate the adsorption strength of the adsorbates, thus achieving the best HER/OER/ORR performance among 216 candidates, and the lowest overpotential of 0.098/0.3/0.46 V and 0.06/0.48/0.45 V, respectively. Additionally, the d-band center, crystal orbital Hamilton population (COHP), and molecular orbitals are used to reveal the OER/ORR activity source. Particularly, the Rh/Ir-d orbital is dramatically hybridized with the O-p orbital of the oxygenated adsorbates, so that the lone-electrons incipiently locate at the antibonding orbital pair up and populate the downward bonding orbital, allowing oxygenated intermediates to be adsorbed onto (TM-NxO4−x)@g-C16N3-H3 appropriately.
中文翻译:
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协调环境建立并调整卓越的协同“基因组”以实现新型三功能(TM-NxO4−x)@g-C16N3-H3:水分解和氧还原反应超高活性的高通量检查
作为能量转换和存储技术的一个突出关注领域,高活性金属基单原子催化剂(SAC)的开发对于寻找替代贵金属的替代品以实现高效、稳定和低成本的氢具有重要意义析氧反应(HER),以及析氧反应(OER)和氧还原反应(ORR)。将配体和配位环境的巨大可调性与丰富的金属基电催化剂相结合,可以为实现高稳定性和活性创造突破性机会。在此,我们提出了一种新型稳定的多孔石墨烯类氮化碳单层 gC 16 N 5 (N 4 @gC 16 N 3)化学计量有趣地充当构建SAC((TM-N 4)@gC 16 N 3)的天然底物,其均匀分布的孔映射丰富且均匀的氮配位位置与富电子孤对电子以锚定过渡金属(TM)原子。然后,我们采用密度泛函理论(DFT)计算系统地研究了(TM-N 4)@gC 16 N 3对HER/OER/ORR的电催化活性,同时考虑H负载和O配位的协同调节( (TM-N x O 4− x )@gC 16 N 3 -H 3 , x= 0–4)。结合“四步法”筛选机制和第一性原理高通量计算,我们发现(Rh-N 4 )和(Ir-N 2 O 2-II )分布在gC 16 N 3 -H 3上可以调节吸附物的吸附强度,从而实现 216 个候选物中最好的 HER/OER/ORR 性能,以及分别为 0.098/0.3/0.46 V 和 0.06/0.48/0.45 V 的最低过电势。此外,d 带中心、晶体轨道汉密尔顿布居 (COHP) 和分子轨道用于揭示 OER/ORR 活性源。特别是,Rh/Ir-d 轨道与氧化吸附物的 Op 轨道显着杂化,因此孤电子最初位于反键轨道对上并填充向下键轨道,从而使氧化中间体被吸附到(适当地为TM-N x O 4− x )@gC 16 N 3 -H 3。