Coordination engineering was employed to optimize the coordination environment of the zirconium (Zr) atom anchored on the porphyrins (PP), serving as single-atom catalysts (SACs). Five promising ZrPP-A (A = C₃O, N₄, N₂C₂-o, C₂O₂-o, and C₂O₂-n) candidates as electrocatalysts for nitrogen reduction reaction (NRR) were identified through a “four-step” screening strategy, from a pool of 15 designed models. Performance evaluation of these candidates for NRR was conducted using first-principles calculations. A comprehensive examination of reaction pathways unveiled a predilection for a hybrid pathway when employing the selected catalysts for the NRR. The stability and notable catalytic activity of ZrPP-A stemmed from orbital hybridization and charge transfer mechanisms, occurring both between Zr and its coordinated atoms, as well as between ZrPP-A and the adsorbed N₂ molecule. Zr played a pivotal role in orchestrating charge transfer during the NRR process. Simultaneously, coordinating atoms and the PP moiety collectively facilitated supplementary charge transfers to or from the adsorbate. Because of the robust coupling between O and its neighboring carbon atoms, no significant bonds were detected between the central Zr and the coordinating O atoms. An asymmetric coordination environment results in an uneven charge distribution within the substrate, inducing polarization of N₂ molecules and their migration toward regions of asymmetric charge aggregation. This study underscores the significance of not only focusing on the single-atom catalyst itself but also its coordination environment when designing catalysts for enhanced efficiency.

中文翻译：

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用于 N2 还原的锆氮功能化材料的配位工程：第一原理模拟


采用配位工程来优化锚定在卟啉（PP）上的锆（Zr）原子的配位环境，作为单原子催化剂（SAC）。五种有前景的ZrPP-A (A = C ₃ O, N ₄ , N ₂ C ₂ -o, C ₂ O ₂ -o 和 C ₂ O ₂ -n) 候选氮还原反应（NRR）电催化剂通过“ “四步”筛选策略，从 15 个设计模型中进行筛选。使用第一性原理计算对这些 NRR 候选者进行性能评估。对反应途径的全面检查揭示了在使用所选催化剂进行 NRR 时对混合途径的偏好。 ZrPP-A 的稳定性和显着的催化活性源于 Zr 与其配位原子之间以及 ZrPP-A 与吸附的 N ₂ 分子之间发生的轨道杂化和电荷转移机制。 Zr 在 NRR 过程中协调电荷转移中发挥着关键作用。同时，配位原子和 PP 部分共同促进补充电荷转移至吸附物或从吸附物转移。由于 O 与其相邻碳原子之间的牢固耦合，在中心 Zr 与配位 O 原子之间没有检测到显着的键。不对称的配位环境导致衬底内电荷分布不均匀，从而引起 N ₂ 分子的极化及其向不对称电荷聚集区域的迁移。这项研究强调了在设计催化剂以提高效率时不仅关注单原子催化剂本身而且关注其配位环境的重要性。