在 Pb 基底上原位生成的水羟铅薄膜上对 CO 进行高选择性电催化还原生成 HCOOH。
Highly selective electrocatalytic reduction of CO to HCOOH over an in situ derived hydrocerussite thin film on a Pb substrate.
机构信息
Key Laboratory of Microbial Technology for Industrial Pollution Control of Zhejiang Province, College of Environment, Zhejiang University of Technology, Hangzhou, 310032, China; School of Environment Science and Spatial Informatics, China University of Mining and Technology, Xuzhou, 221116, China.
Key Laboratory of Microbial Technology for Industrial Pollution Control of Zhejiang Province, College of Environment, Zhejiang University of Technology, Hangzhou, 310032, China.
出版信息
Chemosphere. 2022 Mar;291(Pt 3):132889. doi: 10.1016/j.chemosphere.2021.132889. Epub 2021 Nov 12.
A metal oxide electrode has been developed for the electrochemical CO reduction reaction (eCORR). It exhibits superior activity and product selectivity towards eCORR by circumventing the previously encountered problem of self-reduction with high-valence metals. Specifically, a hydrocerussite [Pb(CO)(OH)] thin film has been synthesized in situ on a Pb substrate (denoted as ER-HC) by an electroreduction method using a lead-based metal-organic framework (Pb-MOF) as a precursor. The ER-HC electrode exhibits a high selectivity of 96.8% towards HCOOH production with a partial current density of 1.9 mA cm at -0.88 V vs. the reversible hydrogen electrode (RHE). A higher HCOOH partial current density of 7.3 mA cm has been achieved at -0.98 V vs. RHE. Physicochemical and electrochemical characterization results demonstrate that the defective hydrocerussite surface exhibits appropriate adsorption free energy of formate (HCOO) and a lower reaction free energy for HCOOH production from CO, which greatly boosts the eCORR activity and HCOOH production selectivity. The structure and eCORR performance of the hydrocerussite thin film remain stable in 0.1 M KHCO as electrolyte, ensuring its durability. Overall, this work not only provides a metal oxide electrode (metal hydroxide, to be more precise) with excellent eCORR performance, but also expands the in situ electrochemical derivatization strategy for the fabrication of metal oxide electrodes.
一种金属氧化物电极已被开发用于电化学 CO 还原反应（eCORR）。它通过规避高价金属自还原的先前遇到的问题，对 eCORR 表现出卓越的活性和产物选择性。具体来说，通过使用基于 Pb 的金属有机骨架（Pb-MOF）作为前体的电还原方法，在 Pb 基底上原位合成了 Pb(CO)(OH) 薄膜（表示为 ER-HC）。ER-HC 电极对 HCOOH 生产具有 96.8%的高选择性，在相对于可逆氢电极（RHE）的-0.88 V 时具有 1.9 mA cm 的部分电流密度。在相对于 RHE 的-0.98 V 时，实现了更高的 HCOOH 部分电流密度 7.3 mA cm。物理化学和电化学表征结果表明，缺陷 Hydrocerussite 表面表现出适当的甲酸盐（HCOO）吸附自由能和较低的 CO 生成 HCOOH 的反应自由能，这极大地提高了 eCORR 活性和 HCOOH 生产选择性。在 0.1 M KHCO 作为电解质的情况下，Hydrocerussite 薄膜的结构和 eCORR 性能保持稳定，确保了其耐用性。总体而言，这项工作不仅提供了具有卓越 eCORR 性能的金属氧化物电极（更确切地说是金属氢氧化物），而且还扩展了用于制造金属氧化物电极的原位电化学衍生策略。
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