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Excellent long-term reactivity of inhomogeneous nanoscale Fe-based metallic glass in wastewater purification

纳米尺度非均匀性诱导自更新铁基非晶合金具有优异的长期反应活性

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Abstract

Metallic glasses (MGs) have attracted great attention in wastewater treatment because of their high reactivity arising from amorphous structure, large residual stress and high density of low coordination sites. However, the reactivity of MGs would gradually slow down with time due to the passivation of active sites by corrosion products, resulting in limited long-term reactivity, which is also an unsolved key issue for established crystalline zero valent iron (ZVI) technology. Here, such problems are successfully overcome by introducing nanoscale chemical inhomogeneities in Fe-based MG (Fe-MGI), which apparently contributes to local galvanic cell effect and accelerates electron transfer during degradation process. More importantly, the selective depletion of Fe0 causes local volume shrinkage and crack formation, leading to self-peeling of precipitated corrosion products and reacted regions. Thereby fresh low coordination sites could be continuously provided, counteracting the mass transport and reactivity deteriorating problem. Consequently, Fe-MGI demonstrates excellent long-term reactivity and self-refreshing properties even in neutral solution. The present results provide not only a new candidate but also a new route of designing ZVI materials for wastewater treatment.

摘要

铁基非晶合金作为亚稳态新型零价铁, 具有高活性亚稳态结构、 较大的残余应力和高密度低配位点等特性, 在催化和废水处理中引起了广泛的关注; 但由于腐蚀产物沉淀覆盖活性位点, 非晶合金的反应活性随着时间的推移而逐渐降低, 导致耐用性差. 腐蚀产物沉淀造成长期反应活性降低也是阻碍传统晶态零价铁技术在废水处理领域应用的主要问题之一. 本文通过在铁基非晶合金中引入纳米尺度的化学不均匀性, 有助于构成局部原电池效应, 加速电子在降解过程中的转移, 可以有效地克服这一问题. 更重要的是, 非晶合金中的零价铁被选择性腐蚀/脱合金, 导致反应区域局部体积收缩和裂纹形成, 裂纹扩展使沉淀腐蚀产物和反应区域自剥落. 因此, 可以连续提供新的低配位, 消除质量传递和反应活性恶化的问题. 本文所制备的具有成分不均匀的铁基非晶合金即使在中性溶液中也具有良好的长期反应活性和自更新性能. 研究结果不仅为废水处理提供了一种新材料, 而且为设计高活性零价铁材料提供了一种新思路.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (NSFC, 51871129 and 51571127), the National Key Basic Research and Development Programme (2016YFB0300502), and the Natural Science Foundation of Jiangsu Province (BK20190480). The author Chen SQ appreciates the help from Heng-Wei Luan, Jia-Cheng Ge, Si-Nan Liu and Dr. Sudheer Kumar Yadav.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Material Science and Engineering, Tsinghua University, Beijing, 100084, China

    Shuang-Qin Chen  (陈双琴), Ke-Zhen Hui  (惠可臻), Liang-Zheng Dong  (董梁正), Wei Zhao  (赵威), Yang Shao  (邵洋) & Ke-Fu Yao  (姚可夫)

  2. Herbert Gleiter Institute of Nanoscience, Nanjing University of Science and Technology, Nanjing, 210094, China

    Shuang-Qin Chen  (陈双琴), Si Lan  (兰司) & Horst Hahn

  3. China Iron & Steel Research Institute Group, Beijing, 100081, China

    Zhun Li  (李准)

  4. Beijing Laboratory for Electron Microscopy, Institute of Physics, CAS, Beijing, 100190, China

    Qing-hua Zhang  (张庆华) & Lin Gu  (谷林)

  5. Institute of Nanotechnology, Karlsruhe Institute of Technology, 76344, Eggenstein-Leopoldshafen, Germany

    Horst Hahn

  6. China Spallation Neutron Source, Institute of High Energy Physics, Chinese Academy of Sciences, Dongguan, 523803, China

    Yubin Ke  (柯于斌)

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  1. Shuang-Qin Chen  (陈双琴)
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  2. Ke-Zhen Hui  (惠可臻)
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Contributions

Author contributions Chen SQ designed and performed most of the experiments and wrote the manuscript with support from Hahn H, Shao Y, Yao KF and Zhao W. Hui KZ and Dong LZ performed the experiments of degradation of azo dyes. Li Z prepared the ribbons. Zhang QH and Gu L performed the TEM experiments. Lan S and Ke Y conducted the SANS experiments. Shao Y, Hahn H and Yao KF conceived and supervised the study. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yang Shao  (邵洋) or Ke-Fu Yao  (姚可夫).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Shuang-Qin Chen received her PhD degree in materials science from Tsinghua University under the supervision of Prof. Kefu Yao in 2018. Currently, she is working at Nanjing University of Science and Technology as an assistant professor. Her present research interests focus on the catalytic properties of metallic glasses.

Yang Shao is an associate professor of the School of Materials Science and Engineering at Tsinghua University. He received his BE degree in 2002 and Master degree in 2004 from Tsinghua University, and received his PhD degree in 2009 from McMaster University. After postdoc research in the Canadian Centre for Electron Microscopy, he joined in Tsinghua University in 2010. Dr. Shao’s research interests mainly focus on the fundamentals and applications of advanced metallic alloys.

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Chen, SQ., Hui, KZ., Dong, LZ. et al. Excellent long-term reactivity of inhomogeneous nanoscale Fe-based metallic glass in wastewater purification. Sci. China Mater. 63, 453–466 (2020). https://doi.org/10.1007/s40843-019-1205-5

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