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Nitrate electroreduction to ammonia over TiO2@C/Fe2O3 nanosheet arrays: Unraveling the impact of hydrothermal carbon

在TiO2@C/Fe2O3纳米片阵列上电还原硝酸根制氨: 揭示水热碳的影响

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Abstract

Electrochemical nitrate reduction to ammonia (NRA) is considered a promising strategy for environmental protection and energy saving because it can simultaneously achieve nitrate wastewater treatment and ammonia synthesis. However, currently, this method suffers from the lack of efficient electrocatalysts. In this work, through a “killing two birds with one stone” strategy, a catalyst, TiO2@C/Fe2O3 nanosheet arrays (NSAs), was fabricated by introducing hydrothermal carbon (HTC), which not only accelerates the charge transfer due to its good conductivity but also provides abundant oxygen vacancies owing to its nice reducibility, finally improving the NRA performance. Compared with TiO2/Fe2O3 NSAs, TiO2@C/Fe2O3 exhibited higher NRA performance with a nitrate conversion of 88.6%, ammonia selectivity of 83.4%, Faradaic efficiency of 85.3%, and ammonia yield of 0.2176 mmol h−1 cm−2. Moreover, the retention of high activity in nine cyclic experiments confirmed the outstanding stability of TiO2@C/Fe2O3. Furthermore, the possible NRA reaction pathway was derived from the results of electrochemical quasi in situ electron spin resonance experiments, electrochemical in situ attenuated total reflection Fourier transform infrared measurement and online differential electrochemical mass spectrometry. This feasible strategy of introducing an HTC interlayer may open new avenues for developing novel NRA electrocatalysts.

摘要

电化学硝酸根还原制氨(NRA)可以同时实现硝酸盐废水处理和氨合成, 是一种很有前途的环保节能策略. 目前构建高效的电催化剂是人们关注的焦点. 本文构建了TiO2@C/Fe2O3纳米片阵列作为高效催化剂, 采用多种表征手段系统研究了水热碳的引入对NRA性能的影响. 我们发现水热碳既可作为良导体实现电荷的快速传递, 又可作为还原剂引入更多的氧空位, 实现了“一石二鸟”催化剂构建策略. 与TiO2/Fe2O3相比, TiO2@C/Fe2O3具有更高的NRA性能, 硝酸盐转化率为88.6%、 氨选择性为8 3. 4 % 、 法拉第效率为8 5. 3 % 、氨收率为0.2176 mmol h−1cm−2. 此外, 在9次循环实验后, TiO2@C/Fe2O3的高活性仍得以保持, 证实了TiO2@C/Fe2O3出色的稳定性. 此外, 我们利用电化学准原位电子自旋共振实验、 电化学原位衰减全反射傅立叶变换红外测量和在线差分电化学质谱法推导了可能的NRA反应途径. 这种引入水热碳中间层的策略可为开发新型NRA电催化剂开辟新的途径.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (21576211), Tianjin Science and Technology Program (22ZYJDSS00060 and 22YDTPJC00920), the Program for Tianjin Innovative Research Team in Universities (TD13-5031), and Tianjin 131 Research Team of Innovative Talents.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Separation Membranes and Membrane Processes, School of Material Science and Technology, Tiangong University, Tianjin, 300387, China

    Xuan Wu  (吴璇), Dan Liu  (刘丹) & Jianzhou Gui  (桂建舟)

  2. Tianjin Key Laboratory of Green Chemical Technology and Process Engineering, School of Chemical Engineering and Technology, Tiangong University, Tianjin, 300387, China

    Aijing Ma  (马爱静), Xueqian Li  (李雪倩) & Jianzhou Gui  (桂建舟)

  3. School of Chemistry, Tiangong University, Tianjin, 300387, China

    Dan Liu  (刘丹) & Yingkang Zhou  (周颖康)

  4. Institute for Nanotechnology and Water Sustainability, College of Science, Engineering and Technology, University of South Africa, Florida, 1709, Johannesburg, South Africa

    Dan Liu  (刘丹), Alex T. Kuvarega, Bhekie B. Mamba & Jianzhou Gui  (桂建舟)

  5. Ningxia Coal Industry Co., Ltd., CHN ENERGY, Yinchuan, 750011, China

    Hu Li  (李虎)

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  1. Xuan Wu  (吴璇)
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Contributions

Author contributions Wu X performed the experiments, analyzed the data and wrote the draft with support from Ma A, Liu D, Li X, Zhou Y and Mamba BB. Kuvarega AT revised the paper. Li H and Gui J supervised the project. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Dan Liu  (刘丹), Hu Li  (李虎) or Jianzhou Gui  (桂建舟).

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

Additional information

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

Xuan Wu is a doctoral candidate at the School of Material Science and Technology, Tiangong University. She graduated from Tiangong University with a Bachelor’s degree in 2018. Her research is focused on the design and synthesis of advanced nanomaterials for electrocatalytic nitrate reduction.

Aijing Ma is an associate professor at the School of Chemical Engineering and Technology, Tiangong University. She received her PhD degree in 2015 from the University of South Australia. She completed her postdoctoral fellowship from Nanyang Technological University, Singapore in 2016 and then joined Tiangong University. Her current research interests mainly focus on the design and synthesis of advanced materials for energy and environmental catalysis.

Dan Liu received her PhD degree from China University of Petroleum. After postdoctoral training at Korea Research Institute of Chemical Technology for three years and a one-year academic visit at Brown University, she is currently a professor at Tiangong University and was awarded Tianjin Distinguished Professor in 2020. Her main research interest focuses on environmental catalysis, low-carbon technology and smart nanomaterials.

Hu Li is a president & senior engineer at the Institute of Coal Chemical Industry Technology, Ningxia Coal Industry Co., Ltd. affiliated to China Energy Group. His research fields range from the coal-to-oil process to diversified indirect coal liquefaction downstream products, e.g., long-chain alcohol and lubricating base oil. He won the Science and Technology Progress Awards from China Petroleum and Chemical Federation (Grand Prize, 2018), CHN Energy (Grand Prize, 2019), and Ningxia Hui Autonomous Region (second prize, 2020).

Jianzhou Gui received his PhD degree from Lanzhou University in 2005, and became a senior visiting scholar at Korea Research Institute of Chemical Technology in 2009. He is currently the dean of Tianjin Key Laboratory of Green Chemical Technology and Process Engineering, and a professor of the School of Chemical Engineering and Technology, Tiangong University. His research interests include petrochemical engineering, green catalysis, adsorption and separation, and functional materials.

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Wu, X., Ma, A., Liu, D. et al. Nitrate electroreduction to ammonia over TiO2@C/Fe2O3 nanosheet arrays: Unraveling the impact of hydrothermal carbon. Sci. China Mater. 66, 4367–4376 (2023). https://doi.org/10.1007/s40843-023-2620-4

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