Pei Yuhou, Li Di, Qiu Chuntian, Yan Liang, Li Zongmiao, Yu Zexin, Fang Wenzhang, Lu Yingying, Zhang Bing
State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, P. R. China.
ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, 311215, P.R. China.
Angew Chem Int Ed Engl. 2024 Nov 25;63(48):e202411977. doi: 10.1002/anie.202411977. Epub 2024 Oct 2.
Electrochemical sulfion oxidation reaction (SOR) offers a sustainable strategy for sulfion-rich wastewater treatment, which can couple with cathodic hydrogen evolution reaction (HER) for energy-saving hydrogen production. However, the corrosion and passivation of sulfur species render the inferior catalytic SOR performance, and the oxidation product, polysulfide, requires further acidification to recover cheap elementary sulfur. Here, we reported an amorphous high-entropy sulfide catalyst of CuCoNiMnCrS nanosheets in situ growth on the nickel foam (CuCoNiMnCrS/NF) for SOR, which achieved an ultra-low potential of 0.25 V to afford 100 mA cm, and stable electrolysis at as high as 1 A cm for 100 h. These were endowed by the manipulated chemical environments surrounding Cu sites and the constructed "soft-acid" to "hard-acid" adsorption/desorption sites, enabling synergistically boosted adsorption/desorption process of sulfur species during SOR. Moreover, we developed an electrochemical-chemical tandem process to convert sulfions to value-added thiosulfate, providing a good choice for simultaneous wastewater utilization and hydrogen production.
电化学硫离子氧化反应（SOR）为富硫废水处理提供了一种可持续策略，该反应可与阴极析氢反应（HER）耦合以实现节能制氢。然而，硫物种的腐蚀和钝化导致催化SOR性能较差，并且氧化产物多硫化物需要进一步酸化以回收廉价的单质硫。在此，我们报道了一种在泡沫镍（CuCoNiMnCrS/NF）上原位生长的用于SOR的非晶态高熵硫化物催化剂CuCoNiMnCrS纳米片，其实现了0.25 V的超低过电位以提供100 mA cm⁻²的电流密度，并在高达1 A cm⁻²的电流密度下稳定电解100小时。这些性能得益于围绕铜位点操控的化学环境以及构建的从“软酸”到“硬酸”的吸附/解吸位点，从而在SOR过程中协同促进硫物种的吸附/解吸过程。此外，我们开发了一种电化学 - 化学串联工艺将硫离子转化为增值的硫代硫酸盐，为同时实现废水利用和制氢提供了一个良好的选择。
