Investigating spin dynamics in electrocatalysis is crucial for the rational design of magnetically heterogeneous catalysts. Utilizing spin-polarized density functional theory calculation, herein, the spin dynamic of diatomic Co₂-supported γ-graphyne (Co₂-GY) catalysts during the process of CO electroreduction (eCORR) is identified, focusing on the effect of the applied potential and acidity on spin dynamic and catalytic performance. In particular, the obtained Co₂-GY shows a new efficient C₂ pathway of CH₂* + CHO* coupling mechanism, resulting in the optimal CH₃CH₂OH product with ∆G of 0.50 eV and the selectivity of 99.99% under alkaline conditions. Under acidic media, Co₂-GY exhibits the optimal C₁ product (CH₃OH) with ∆G of 0.27 eV and a selectivity of 99.99%. During CO electroreduction, the reaction environment (pH and applied potential) influences spin dynamics in catalyst-reactant systems, affecting the spin transition of diatomic Co₂ active sites among four magnetic states: ferromagnetic, antiferromagnetic, paramagnetic, and diamagnetic. These findings will be helpful for the rational design of transition-metal heterogeneous catalysts.

中文翻译：

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探索石墨烯上双原子 Co2 催化剂的自旋动力学以增强 Co 电还原

研究电催化中的自旋动力学对于磁多相催化剂的合理设计至关重要。利用自旋极化密度泛函理论计算，本文确定了双原子 Co2 负载 γ-石墨烯 (Co ₂ -GY) 催化剂在 CO 电还原 (eCORR) 过程中的自旋动力学，重点关注了外加电位和酸性对自旋动力学和催化性能的影响。特别是，所获得的Co ₂ -GY显示了CH ₂ * + CHO*偶联机制的新的高效C ₂途径，产生了最佳的CH ₃ CH ₂ OH产物，ΔG为0.50 eV，碱性条件下选择性为99.99%状况。在酸性介质下，Co ₂ -GY 表现出最佳的 C ₁产物（CH ₃ OH），ΔG 为 0.27 eV，选择性为 99.99%。在CO电还原过程中，反应环境（pH值和施加电势）影响催化剂-反应物系统中的自旋动力学，影响双原子Co ₂活性位点在四种磁态之间的自旋转变：铁磁、反铁磁、顺磁和反磁。这些发现将有助于过渡金属多相催化剂的合理设计。