Hierarchically Ordered Pore Engineering of Carbon Supports with High-Density Edge-Type Single-Atom Sites to Boost Electrochemical CO2 Reduction,Advanced Materials

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Hierarchically Ordered Pore Engineering of Carbon Supports with High-Density Edge-Type Single-Atom Sites to Boost Electrochemical CO2 Reduction
Advanced Materials ( IF 27.4 ) Pub Date : 2024-10-03 , DOI: 10.1002/adma.202409531
Chenghong Hu ₁ , Ximeng Hong ₁ , Miaoling Liu ₁ , Kui Shen ₁ , Liyu Chen ₁ , Yingwei Li ₁

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Metal sites at the edge of the carbon matrix possess unique geometric and electronic structures, exhibiting higher intrinsic activity than in-plane sites. However, creating single-atom catalysts with high-density edge sites remains challenging. Herein, the hierarchically ordered pore engineering of metal–organic framework-based materials to construct high-density edge-type single-atomic Ni sites for electrochemical CO₂ reduction reaction (CO₂RR) is reported. The created ordered macroporous structure can expose enriched edges, further increased by hollowing the pore walls, which overcomes the low edge percentage in the traditional microporous substrates. The prepared single-atomic Ni sites on the ordered macroporous carbon with ultra-thin hollow walls (Ni/H-OMC) exhibit Faraday efficiencies of CO above 90% in an ultra-wide potential window of 600 mV and a turnover frequency of 3.4 × 10⁴ h⁻¹, much superior than that of the microporous material with dominant plane-type sites. Theory calculations reveal that NiN₄ sites at the edges have a significantly disrupted charge distribution, forming electron-rich Ni centers with enhanced adsorption ability with ^*COOH, thereby boosting CO₂RR efficiency. Furthermore, a Zn–CO₂ battery using the Ni/H-OMC cathode shows an unprecedentedly high power density of 15.9 mW cm⁻² and maintains an exceptionally stable charge–discharge performance over 100 h.

中文翻译：

具有高密度边缘型单原子位点的碳载体的分层有序孔隙工程，以促进电化学 CO2 还原

碳基体边缘的金属位点具有独特的几何和电子结构，表现出比面内位点更高的内禀活性。然而，创建具有高密度边缘位点的单原子催化剂仍然具有挑战性。在此，报道了基于金属有机框架的材料进行分层有序孔工程，以构建用于电化学 CO₂ 还原反应（CO₂RR）的高密度边缘型单原子 Ni 位点。创建的有序大孔结构可以暴露出丰富的边缘，通过挖空孔壁进一步增加，这克服了传统微孔基材的低边缘百分比。在具有超薄空心壁（Ni/H-OMC）的有序大孔碳上制备的单原子 Ni 位点在 600 mV 的超宽电位窗口和 3.4 ×^{10 4} ^h-1 的周转频率中表现出 CO 的法拉第效率超过 90%，远优于具有优势平面型位点的微孔材料。理论计算表明，边缘的 NiN₄ 位点具有显着的电荷分布中断，形成富含电子的 Ni 中心，具有增强的 ^*COOH 吸附能力，从而提高 CO₂RR 效率。此外，使用 Ni/H-OMC 阴极的 Zn-CO₂ 电池显示出前所未有的 15.9 mW ^cm-2 功率密度，并在 100 小时内保持异常稳定的充放电性能。

更新日期：2024-10-03

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