Guo Yiming, Xu Yong, Chen Pengzuo
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China.
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, Zhejiang, China.
J Colloid Interface Sci. 2025 Dec;699(Pt 2):138292. doi: 10.1016/j.jcis.2025.138292. Epub 2025 Jun 27.
The development of high-performance electrocatalysts for the valorization of surplus glycerol into high-value-added chemicals using renewable electricity is of great significance for a sustainable economy. However, significant challenges remain in maintaining efficient production of target products at ampere-level current densities. Herein, we successfully constructed crystalline/amorphous CoO@ZrO heterostructured nanosheets in situ on nickel foam (NF) substrate. This unique architecture exposes abundant active sites while the coupled crystalline/amorphous electronic interaction enhances interfacial charge transport, thereby endowing the catalyst with exceptional performance for glycerol electrooxidation to formate. Remarkably, the optimized CoO@ZrO/NF achieves an ampere-level current density of 1 A cm at a low potential of 1.5 V vs. RHE, while delivering an impressive Faradaic efficiency of formate over 90 % across a wide range of 0.4-1.0 A cm. In situ spectroscopic studies reveal that the crystalline/amorphous heterostructure facilitates the dynamic reconstruction of active species and significantly promoted the reaction kinetics for glycerol oxidation. Furthermore, when employed in a two-electrode system, the electrolyzer demonstrates efficient Faradaic efficiency of H (nearly 100 %) and formate yield (11.99 mmol h cm at 1 A cm), as well as exceptional stability over 100 h at 100 mA cm.
开发高性能电催化剂，利用可再生电力将过剩甘油转化为高附加值化学品，对可持续经济具有重要意义。然而，在安培级电流密度下维持目标产物的高效生产仍面临重大挑战。在此，我们成功地在泡沫镍（NF）基底上原位构建了晶体/非晶态CoO@ZrO异质结构纳米片。这种独特的结构暴露了丰富的活性位点，同时晶体/非晶态电子耦合相互作用增强了界面电荷传输，从而赋予该催化剂在甘油电氧化制甲酸盐方面的卓越性能。值得注意的是，优化后的CoO@ZrO/NF在相对于可逆氢电极（RHE）为1.5 V的低电位下实现了1 A cm²的安培级电流密度，同时在0.4 - 1.0 A cm²的宽范围内提供了超过90%的令人印象深刻的甲酸盐法拉第效率。原位光谱研究表明，晶体/非晶态异质结构促进了活性物种的动态重构，并显著促进了甘油氧化的反应动力学。此外，当应用于两电极系统时，该电解槽展示了高效的氢气法拉第效率（接近100%）和甲酸盐产率（在1 A cm²时为11.99 mmol h⁻¹ cm⁻²），以及在100 mA cm⁻²下超过100小时的卓越稳定性。
