<br>揭示 CoWO4 在电催化硝酸盐还原反应中的表面重构,Chemical Engineering Journal

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揭示 CoWO4 在电催化硝酸盐还原反应中的表面重构
Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2024-12-20 , DOI: 10.1016/j.cej.2024.158819
Qingna Gong , Han Zhao , Wen-Da Zhang , Jing-Dong Feng , Yiguo Zhang , Ying Zhang , Jiangyong Liu , Bing Liu , Jiangwei Zhang , Xiaoping Yang , Jing Wang , Xiaodong Yan

探索操作条件下的结构动力学对于理解结构-功能关系至关重要。在此，我们选择钨酸钴（CoWO4）进行电化学硝酸盐还原反应（NO3RR），并发现阴离子浸出诱导表面重构显着增强了催化活性的现象，这在 NO3RR 中很少报道。正如原位 X 射线吸收、拉曼和紫外-可见光谱所证明的那样，CoWO4 的表面重建是由 WO42- 浸出触发的，导致 CoOOH 表层的出现。随着表面 CoOOH 层的形成，核壳 CoWO4/CoOOH 异质结构表现出显着的 NO3RR 活性，在 -0.426 V 下与 RHE 相比，NH3 产率高达 3.82 mmol h-1 cm-2。原位 X 射线吸收光谱显示，CoOOH 增强了含 N 中间体的吸收和氢化，而密度函数理论计算证实，内部 CoWO4 在 NO3RR 期间提供 *H。此外，CoWO4/CoOOH 降低了速率确定步骤的自由能势垒，促进了 NH3 的解吸。本研究提出了一种研究动态重建过程的系统方法，并为阴离子浸出诱导的表面重建提供了有价值的见解。

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Unveiling the surface reconstruction of CoWO4 on electrocatalytic nitrate reduction reaction

Exploring the structural dynamics under operational conditions is crucial for understanding the structure–function relationship. Herein, we select cobalt tungstate (CoWO4) for electrochemical nitrate reduction reaction (NO3RR), and find a phenomenon that anion leaching induced surface reconstruction significantly enhances the catalytic activity, which has rarely been reported in NO3RR. As demonstrated by in situ X-ray absorption, Raman, and ultraviolet–visible spectroscopies, the surface reconstruction of CoWO4 is triggered by WO42- leaching, resulting in the emergence of CoOOH surface layer. With the formation of the surface CoOOH layer, the core–shell CoWO4/CoOOH heterostructure exhibits remarkable NO3RR activity with a high NH3 yield rate of 3.82 mmol h−1 cm−2 at −0.426 V vs. RHE. In situ X-ray absorption spectra reveal that the CoOOH enhances the absorption and hydrogenation of N-containing intermediates, while density function theory calculations confirm that the internal CoWO4 supplies *H during NO3RR. Additionally, the CoWO4/CoOOH reduces the free energy barrier of the rate-determining step, facilitating the desorption of NH3. This study presents a systematic approach to study the dynamic reconstruction process and offers valuable insights into anion leaching induced surface reconstruction.

更新日期：2024-12-20

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