The electrochemical CO₂ reduction reaction (CO₂RR) offers a promising pathway to convert CO₂ into value-added chemicals, with CO production being a primary target. While the conversion of CO₂ to CO hinges on the delicate balance of *COOH and *CO binding energies, this study introduces a series of Pd-based hybrid catalysts, Me₁₀CB[5]–M/Pd (M = Sr, Ca, and Cd), to address this challenge. The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me₁₀CB[5], M²⁺, and [PdCl₄]²⁻ ions. Notably, Me₁₀CB[5]–Sr/Pd exhibited exceptional CO selectivity (91.3% FE_CO at −0.7 V vs. RHE) and long-term stability. The incorporation of Me₁₀CB[5]–Sr into the Pd catalyst system enhanced CO₂ adsorption, modulated the electronic structure of Pd, and optimized the adsorption/desorption energies of critical intermediates, ultimately leading to superior CO₂RR performance. This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO₂ conversion.

中文翻译：

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用十甲基葫芦[5]尿基-碱土金属改性的 Pd 纳米颗粒增强 CO2 电还原


电化学 CO₂ 还原反应 （CO₂RR） 为将 CO₂ 转化为增值化学品提供了一条有前途的途径，其中 CO 生产是主要目标。虽然 CO₂ 到 CO 的转化取决于 *COOH 和 *CO 结合能的微妙平衡，但本研究引入了一系列基于 Ple 的杂化催化剂 Me₁₀CB[5]–M/Pd（M = Sr、Ca 和 Cd）来应对这一挑战。催化剂是通过对由 Me₁₀CB[5]、M²⁺ 和 [PdCl₄]²⁻ 离子形成的超分子前驱体进行热处理合成的。值得注意的是，Me₁₀CB[5]–Sr/Pd 表现出优异的 CO 选择性（在 -0.7 V 与 RHE 时为 91.3% FE_CO）和长期稳定性。将 Me₁₀CB[5]-Sr 掺入 Pd 催化剂体系中增强了 CO 2 吸附，调节了_Pd 的电子结构，并优化了关键中间体的吸附/解吸能，最终实现了卓越的 CO₂RR 性能。这项工作强调了超分子工程在设计用于 CO₂ 转化的高性能电催化剂方面的潜力。