Enhancing CO2 catalytic activation and direct electroreduction on in-situ exsolved Fe/MnOx nanoparticles from (Pr,Ba)2Mn2-yFeyO5+δ layered perovskites for SOEC cathodes
Enhancing CO2 catalytic activation and direct electroreduction on in-situ exsolved Fe/MnOx nanoparticles from (Pr,Ba)2Mn2-yFeyO5+δ layered perovskites for SOEC cathodes
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增强 SOEC 阴极 (Pr,Ba)2Mn2-yFeyO5 δ 层状钙钛矿原位溶解 Fe/MnOx 纳米颗粒的 CO2 催化活化和直接电还原
DOI：
10.1016/j.apcatb.2019.118389
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通讯作者：
Bo Yu
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作者：
Jianxin Zhu;Wenqiang Zhang;Yifeng Li;Wangxu Yue;Ga Geng;Bo Yu
在固体氧化物电解电池（SOECs）中，具有纳米过渡金属颗粒的钙钛矿基氧化物是一种很有前途的直接电催化还原CO2的阴极材料。本文采用一种简便的方法在双层钙钛矿（Pr，Ba）2Mn2-yFeyO5 + δ衬底上原位生长Fe/MnOx纳米粒子，并结合实验表征和第一性原理计算研究了其增强CO2催化活性的机理。在（Pr，Ba）Mn_（1-x）Fe_xO_（3-δ）中引入A位缺陷，可以促进Fe的原位溶出，使其从非自发过程转变为自发过程。Fe颗粒对CO2直接电解具有显著的强化作用，在1.60 V下电流密度为638 mA/cm2。这种增强归因于CO2化学吸附的促进，以及电子从出溶的纳米颗粒到CO2的转移的便利。
Perovskite-based oxides with exsolved nanoscale transition metal particles are promising cathode materials for direct electrocatalytic reduction of CO2in the conversion from electrical power to chemical energy through solid oxide electrolysis cells (SOECs). In this paper, a facile method for thein-situgrowth of Fe/MnOxnanoparticles from double-layered perovskite (Pr,Ba)2Mn2-yFeyO5+δ substrate was developed and the mechanism of enhanced CO2catalytic activation was studied by combined experimental characterization and first-principle calculations. We have showed that introducing A-site deficiencies in (Pr,Ba)Mn1-xFexO3-δ can promotein-situexsolution of Fe from a nonspontaneous process to a spontaneous one thermodynamically. The exsolved Fe particles exhibit significantly enhancement effect, contributing to a highly catalytic performance of direct CO2electrolysis (638 mA/cm2current density under 1.60 V). Such an enhancement is attributed to the promotion of CO2chemical adsorption, as well as the facilitation of electron transfer from the exsolved nano-particles to CO2.