The catalytic activity and selectivity of CO₂ reduction reaction (CO₂RR) towards C1 and C2 products are fundamentally restricted by the inherent linear scaling relationship among the adsorption-free energies of intermediates. To face this challenge, we have proposed a novel multifunctional M₁M₂@BN electrocatalysts to break the linear scaling relationships in CO₂RR and efficiently obtain C1 and C2 products. Our results reveal that the optimal limiting potential is increased from −0.58 V for M@BN to −0.39 V for M₁M₂@BN, which achieves ultrahigh activity of CO₂RR. Further mechanism analysis illuminates that M₁M₂@BN can selectivity modulate the adsorption strength of OCHO* and OCH₂O*/OCHOH*, breaking the linear scaling relationship of adsorption-free energies of key intermediates to achieve the enhanced catalytic activity. Notably, the sufficient active sites on M₁M₂@BN electrocatalysts can promote the sluggish C–C coupling by capturing two CO intermediates simultaneously, further generating high-value multi-carbon (CH₂CH₂OH) products. Meanwhile, the thermodynamic stability of M₁M₂@BN has been demonstrated by ab initio molecular dynamics (AIMD) simulations, which shows the feasibility of commercial application in CO₂RR. Our findings provide a novel strategy to modulate the binding strength of intermediates and develop the design of efficient multi-active-site CO₂RR electrocatalysts.

中文翻译：

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打破 BN 负载金属催化剂中的线性结垢关系，实现对 C1 和 C2 产物的高效 CO2RR


CO₂ 还原反应 （CO₂RR） 对 C1 和 C2 产物的催化活性和选择性从根本上受到中间体无吸附能之间固有的线性缩放关系的限制。为了应对这一挑战，我们提出了一种新型多功能 M₁M₂@BN 电催化剂，以打破 CO₂RR 中的线性缩放关系，高效获得 C1 和 C2 产物。我们的结果表明，最佳限制电位从 M@BN 的 -0.58 V 增加到 M₁M₂@BN 的 -0.39 V，从而实现了 CO₂RR 的超高活性。进一步的机理分析表明，M₁M₂@BN 可以选择性调节 OCHO* 和 OCH₂O*/OCHOH* 的吸附强度，打破关键中间体的无吸附能的线性缩放关系，以实现增强的催化活性。值得注意的是，M₁M₂@BN 电催化剂上足够的活性位点可以通过同时捕获两个 CO 中间体来促进缓慢的 C-C 偶联，从而进一步产生高价值的多碳 （CH₂CH₂OH） 产物。同时，从头计算分子动力学 （AIMD） 模拟证明了 M₁M₂@BN 的热力学稳定性，显示了在 CO₂RR 中商业应用的可行性。我们的研究结果提供了一种新的策略来调节中间体的结合强度，并开发了高效的多活性位点 CO₂RR 电催化剂的设计。