Electrochemical reduction of carbon dioxide into value-added products is expected to be a promising approach to mitigate climate and energy crises. However, the inert nature of CO₂ molecules and the lack of effective electrocatalysts pose fundamental challenges that hinder electrochemical CO₂ reduction. In this work, density functional theory was employed to explore a series of dual-atom catalysts (DACs) supported on four-type nitrogen-doped graphene for the CO₂ reduction reaction (CO₂RR). Based on the correlation between the adsorption free energies of the reaction intermediates, we find that the scaling relations in the multi-intermediate reactions still persist, which distinguishes them from previous studies. In addition, we construct a universal descriptor based on the intrinsic properties of catalysts, which can well assess the catalytic activity of different transition metal dual-atoms on different supports for the CO₂RR. Finally, the constant potential calculation reveals that the adsorption of *CO₂^– exhibits insensitivity toward changes in applied potential for CoCo-3A DACs. The thermochemical step was found to be the limiting step at a low electrode potential. This research elucidates the underlying principles of reaction mechanisms and simultaneously furnishes a systematic framework for expedited exploration of proficient catalysts.

中文翻译：

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电化学二氧化碳还原双原子催化剂的理论见解

将二氧化碳电化学还原为增值产品预计将成为缓解气候和能源危机的一种有前景的方法。然而，CO ₂分子的惰性和缺乏有效的电催化剂构成了阻碍电化学CO ₂还原的根本挑战。在这项工作中，采用密度泛函理论探索了一系列负载在四种氮掺杂石墨烯上的双原子催化剂（DAC）用于CO ₂还原反应（CO ₂ RR）。基于反应中间体吸附自由能之间的相关性，我们发现多中间体反应中的标度关系仍然存在，这与之前的研究不同。此外，我们基于催化剂的固有性质构建了一个通用描述符，可以很好地评估不同过渡金属双原子在不同载体上对CO ₂ RR的催化活性。最后，恒定电势计算表明，*CO ₂ ^–的吸附对 CoCo-3A DAC 施加的电势变化不敏感。发现热化学步骤是低电极电势下的限制步骤。这项研究阐明了反应机制的基本原理，同时为加快探索高效催化剂提供了系统框架。