Enhanced the Efficiency of Electrocatalytic CO2 -to-CO Conversion by Cd Species Anchored into Metal-Organic Framework.
Enhanced the Efficiency of Electrocatalytic CO2 -to-CO Conversion by Cd Species Anchored into Metal-Organic Framework.
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金属有机骨架中的镉物种增强了电催化CO2转化为CO的效率。
DOI：
10.1002/smll.202301319
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发表时间：
2023-05
期刊：
影响因子：
13.3
通讯作者：
Jie Yang;Jing-Yu Yu-Jing-Yu-Yu-2151481958;Weiwei Dong;Dexin Yang;Zhixin Hua;Xiaoqi Wan;Mingyan Wang;Hongping Li
中科院分区：
文献类型：
--
作者：
Jie Yang;Jing-Yu Yu-Jing-Yu-Yu-2151481958;Weiwei Dong;Dexin Yang;Zhixin Hua;Xiaoqi Wan;Mingyan Wang;Hongping Li
金属-有机骨架材料（MOFs）作为一种很有前途的CO2电催化转化平台，其转化效率低或产物选择性不理想，成为制约MOFs发展的瓶颈。本文报道了具有Cd位的锆基卟啉MOF中空纳米管（Cd-PCN-222 HTs）用于电催化CO2转化为CO。分散的Cd物种锚定在PCN-222 HTs和卟啉结构的N原子的配位。结果表明，Cd-PCN-222 HTs在离子液体-水（H2O）-乙腈（MeCN）电解液中对选择性CO生成具有良好的电催化活性。CO法拉第效率（FECO）在-2.0 ~-2.4V（相对于Ag/Ag+）的较宽电位范围内均可保持在>80%，在-2.4V（相对于Ag/Ag+）时最大电流密度可达68.0mA cm-2，转换频率为26220 h-1。Cd-PCN-222 HTs的CO2电催化转化效率的提高与其中空结构、锚定的Cd物种以及与电解质良好的协同效应密切相关。密度泛函理论计算结果表明，分散在PCN-222 HTs上的Cd位不仅有利于 *COOH中间体的形成，而且阻碍了析氢反应，从而提高了CO2 -到CO的电催化转化活性.
Metal-organic frameworks (MOFs) as a promising platform for electrocatalytic CO2 conversion are still restricted by the low efficiency or unsatisfied selectivity for desired products. Herein, zirconium-based porphyrinic MOF hollow nanotubes with Cd sites (Cd-PCN-222HTs) are reported for electrocatalytic CO2 -to-CO conversion. The dispersed Cd species are anchored in PCN-222HTs and coordinated by N atoms of porphyrin structures. It is discovered that Cd-PCN-222HTs have glorious electrocatalytic activity for selective CO production in ionic liquid-water (H2 O)-acetonitrile (MeCN) electrolyte. The CO Faradaic efficiency (FECO ) of >80% could be maintained in a wide potential range from -2.0 to -2.4 V versus Ag/Ag+ , and the maximum current density could reach 68.0 mA cm-2 at -2.4 V versus Ag/Ag+ with a satisfied turnover frequency of 26 220 h-1 . The enhanced efficiency of electrocatalytic CO2 conversion of Cd-PCN-222HTs is closely related to its hollow structure, anchored Cd species, and good synergistic effect with electrolyte. The density functional theory calculations indicate that the dispersed Cd sites anchored in PCN-222HTs not only favor the formation of *COOH intermediate but also hinder the hydrogen evolution reaction, resulting in high activity of electrocatalytic CO2 -to-CO conversion.