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Self-template synthesis of hierarchically structured Co3O4@NiO bifunctional electrodes for selective nitrate reduction and tetrahydroisoquinolines semi-dehydrogenation

自模板法合成等级结构Co3O4@NiO双功能电极用 于选择性硝酸根还原和四氢异喹啉类半脱氢

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Abstract

The rational design and synthesis of hierarchically hollow nanostructures with controlled spatial architecture and composition are significant in electrocatalysis owing to their abundant active sites and the expedited electron/mass transfer. Electrocatalytic nitrate reduction to ammonia is of great interest from the points of environmental protection and energy saving. However, the development of this technology is hindered by the lack of efficient nitrate-to-ammonia electrocatalysts and the kinetically sluggish oxygen evolution reaction at the anode. Herein, a novel self-template conversion method was developed for the synthesis of Co3 O4@NiO hierarchical nanotubes (Co3O4@NiO HNTs) with NiO porous nanosheets assembled on Co3O4 nanotubes. The as-obtained Co3O4@NiO HNTs exhibited an outstanding performance for both the cathodic nitrate electroreduction to ammonia reaction and the anodic tetrahydroisoquinolines (THIQs) semi-dehydrogenation to dihydroisoquinolines (DHIQs). Importantly, a two-electrode system of Co3O4@NiO HNTs ∥ Co3O4@NiO HNTs was constructed for the simultaneous synthesis of ammonia and DHIQs with high selectivity and robust stability.

摘要

等级中空结构的纳米材料具有丰富的活性位点和畅通的电 子/物质传递通道, 因此在电催化领域具有广阔的应用前景. 从环保 和节能的角度考虑, 电催化硝酸根还原合成铵具有重要意义. 高效 电催化剂短缺, 以及动力学缓慢的阳极析氧反应, 严重限制了该技 术的发展. 本论文发展了一种新颖的自模板转化法, 将无机有机杂 化的钴基纳米棒成功转化为Co3O4纳米管@NiO多孔纳米片等级材 料. 该材料在阴极硝酸根电还原为铵和阳极四氢异喹啉类半脱氢 为二氢异喹啉类物质的反应中均表现出了优异的性能. 更重要的 是, 合成的Co3O4@NiO等级纳米管还可作为双功能电极, 同时合成 铵和二氢异喹啉化合物, 并具有良好的的选择性和稳定性.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (21701122 and 21871206).

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Authors and Affiliations

  1. Department of Chemistry, School of Science, Institute of Molecular Plus, Tianjin University, Tianjin, 300072, China

    Yuting Wang  (王雨婷), Cuibo Liu  (刘翠波), Bin Zhang  (张兵) & Yifu Yu  (于一夫)

  2. Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Tianjin University, Tianjin, 300072, China

    Bin Zhang  (张兵)

Authors
  1. Yuting Wang  (王雨婷)
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  2. Cuibo Liu  (刘翠波)
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  3. Bin Zhang  (张兵)
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  4. Yifu Yu  (于一夫)
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Contributions

Yu Y and Liu C conceived and directed the project. Wang Y carried out the experiments and wrote the paper. Zhang B revised the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Cuibo Liu  (刘翠波) or Yifu Yu  (于一夫).

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Conflict of interest

The authors declare no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Yuting Wang received her BE degree in applied chemistry from Qingdao University of Science and Technology in 2016. She is currently working on her PhD degree at Tianjin University under the supervision of Prof. Bin Zhang. Her research focuses on the development of electrocatalysts for nitrogen cycle reactions.

Cuibo Liu obtained his PhD from Tianjin University in 2015 (supervised by Prof. Bin Zhang). After that, he joined Prof. Kian Ping Loh’s group at the National University of Singapore for his postdoctoral research. He is now an associate professor at Tianjin University. His research interests are mainly focused on photocatalysis, single-atom-catalysis, as well as electrocatalysis by using nanomaterials for selective synthesis of labelled molecules and energy storage.

Yifu Yu received his BE and PhD degrees in chemical engineering from Tianjin University. He carried out postdoctoral research in Nanyang Technological University under the direction of Prof. Hua Zhang (July 2014 to July 2017). Currently, he is a professor in the Department of Chemistry at Tianjin University. His research interests focus on artificial nitrogen cycle.

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40843_2020_1365_MOESM1_ESM.pdf

Self-template synthesis of hierarchically structured Co3O4@NiO bifunctional electrodes for selective nitrate reduction and tetrahydroisoquinolines semi-dehydrogenation

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Wang, Y., Liu, C., Zhang, B. et al. Self-template synthesis of hierarchically structured Co3O4@NiO bifunctional electrodes for selective nitrate reduction and tetrahydroisoquinolines semi-dehydrogenation. Sci. China Mater. 63, 2530–2538 (2020). https://doi.org/10.1007/s40843-020-1365-0

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