High-performance red mud as an electrocatalyst for nitrate reduction toward ammonia synthesis

doi:10.1016/j.cjche.2024.09.027

中国化学工程学报 ›› 2025, Vol. 77 ›› Issue (1): 195-202.DOI: 10.1016/j.cjche.2024.09.027

High-performance red mud as an electrocatalyst for nitrate reduction toward ammonia synthesis

Qiannan Wang¹, Aaron S. Pittman^2,3,4,5, Yan Cao^1,2,3,4,5

1. College of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China;
2. School of Energy Science and Engineering, University of Science and Technology of China, Guangzhou 510640, China;
3. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
4. CAS Key Laboratory of Renewable Energy, Guangzhou 510640, China;
5. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

收稿日期:2024-04-26 修回日期:2024-09-18 接受日期:2024-09-19 出版日期:2025-01-28 发布日期:2024-11-13
通讯作者: Yan Cao,E-mail:caoyan@ms.giec.ac.cn
基金资助:
This work was supported by grants from the National Natural Science Foundation of China (22178339), 2023 Innovation-driven Development Special Foundation of Guangxi Province (AA23023021) and the Hundred Talents Program (A) of the Chinese Academy of Sciences.

High-performance red mud as an electrocatalyst for nitrate reduction toward ammonia synthesis

Qiannan Wang¹, Aaron S. Pittman^2,3,4,5, Yan Cao^1,2,3,4,5

1. College of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China;
2. School of Energy Science and Engineering, University of Science and Technology of China, Guangzhou 510640, China;
3. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
4. CAS Key Laboratory of Renewable Energy, Guangzhou 510640, China;
5. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China

Received:2024-04-26 Revised:2024-09-18 Accepted:2024-09-19 Online:2025-01-28 Published:2024-11-13
Contact: Yan Cao,E-mail:caoyan@ms.giec.ac.cn
Supported by:
This work was supported by grants from the National Natural Science Foundation of China (22178339), 2023 Innovation-driven Development Special Foundation of Guangxi Province (AA23023021) and the Hundred Talents Program (A) of the Chinese Academy of Sciences.

摘要/Abstract

摘要： Red mud (RM) is a solid waste generated in the aluminum industry after the extraction of alumina oxide; its multiple elements and higher pH value likely pose a severe threat to the environment after treatment. However, RM's higher concentrations of metal components, particularly Fe₂O₃ and rare earth elements (REEs), render RM promising for catalytic application. Hence, this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction (NARR). RM calcined at 500 ℃ (RM-500) exhibited excellent catalytic performance. Faradaic efficiency of ammonia (FE_NH₃) in an electrolyte solution containing 1 mol·L^-¹ NO₃^- achieved a maximum value of 92.3% at -0.8 V (vs. RHE). Additionally, 24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR. The RM-500 demonstrated a high FE of NH₃-to-NO₃^- of 89.7% at 1.85 V (vs. RHE), showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.

关键词: Ammonia synthesis, Nitrate reduction, Red mud, Electrocatalyst, Stability

Abstract: Red mud (RM) is a solid waste generated in the aluminum industry after the extraction of alumina oxide; its multiple elements and higher pH value likely pose a severe threat to the environment after treatment. However, RM's higher concentrations of metal components, particularly Fe₂O₃ and rare earth elements (REEs), render RM promising for catalytic application. Hence, this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction (NARR). RM calcined at 500 ℃ (RM-500) exhibited excellent catalytic performance. Faradaic efficiency of ammonia (FE_NH₃) in an electrolyte solution containing 1 mol·L^-¹ NO₃^- achieved a maximum value of 92.3% at -0.8 V (vs. RHE). Additionally, 24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR. The RM-500 demonstrated a high FE of NH₃-to-NO₃^- of 89.7% at 1.85 V (vs. RHE), showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.

Key words: Ammonia synthesis, Nitrate reduction, Red mud, Electrocatalyst, Stability

Qiannan Wang, Aaron S. Pittman, Yan Cao. High-performance red mud as an electrocatalyst for nitrate reduction toward ammonia synthesis[J]. 中国化学工程学报, 2025, 77(1): 195-202.

Qiannan Wang, Aaron S. Pittman, Yan Cao. High-performance red mud as an electrocatalyst for nitrate reduction toward ammonia synthesis[J]. Chinese Journal of Chemical Engineering, 2025, 77(1): 195-202.

参考文献

[1] S.B. Wang, H.M. Ang, M.O. Tade, Novel applications of red mud as coagulant, adsorbent and catalyst for environmentally benign processes, Chemosphere 72(11) (2008) 1621-1635.
[2] X.F. Kong, M. Li, S.G. Xue, W. Hartley, C.R. Chen, C. Wu, X.F. Li, Y.W. Li, Acid transformation of bauxite residue: conversion of its alkaline characteristics, J. Hazard Mater. 324(Pt B) (2017) 382-390.
[3] M.F. Wang, X.M. Liu, Applications of red mud as an environmental remediation material: a review, J. Hazard Mater. 408(2021) 124420.
[4] Y. Pontikes, G.N. Angelopoulos, Bauxite residue in cement and cementitious applications: current status and a possible way forward, Resour. Conserv. Recycl. 73(2013) 53-63.
[5] X.W. Cheng, D. Long, C. Zhang, X.S. Gao, Y.J. Yu, K.Y. Mei, C.M. Zhang, X.Y. Guo, Z.W. Chen, Utilization of red mud, slag and waste drilling fluid for the synthesis of slag-red mud cementitious material, J. Clean. Prod. 238(2019) 117902.
[6] P.F. Wu, X.M. Liu, Z.Q. Zhang, C. Wei, J. Wang, J.R. Gu, The harmless and value-added utilization of red mud: recovering iron from red mud by pyrometallurgy and preparing cementitious materials with its tailings, J. Ind. Eng. Chem. 132(2024) 50-65.
[7] M. Samouhos, M. Taxiarchou, P.E. Tsakiridis, K. Potiriadis, Greek “red mud” residue: a study of microwave reductive roasting followed by magnetic separation for a metallic iron recovery process, J. Hazard Mater. 254-255(2013) 193-205.
[8] R.B. Li, T.A. Zhang, Y. Liu, G.Z. Lv, L.Q. Xie, Calcification-carbonation method for red mud processing, J. Hazard Mater. 316(2016) 94-101.
[9] D.Y. Wei, J.H. Xiao, Y. Peng, S.Y. Shen, C. Tao, K. Zou, Z. Wang, Extraction of scandium and iron from red mud, Miner. Process. Extr. Metall. Rev. 43(2020) 61-68.
[10] Y.M. Hua, K.V. Heal, W. Friesl-Hanl, The use of red mud as an immobiliser for metal/metalloid-contaminated soil: a review, J. Hazard Mater. 325(2017) 17-30.
[11] J. Yang, H.F. Qi, A.Q. Li, X.Y. Liu, X.F. Yang, S.X. Zhang, Q. Zhao, Q.K. Jiang, Y. Su, L.L. Zhang, J.F. Li, Z.Q. Tian, W. Liu, A.Q. Wang, T. Zhang, Potential-driven restructuring of Cu single atoms to nanoparticles for boosting the electrochemical reduction of nitrate to ammonia, J. Am. Chem. Soc. 144(27) (2022) 12062-12071.
[12] F.Y. Chen, Z.Y. Wu, S. Gupta, D.J. Rivera, S.V. Lambeets, S. Pecaut, J.Y.T. Kim, P. Zhu, Y.Z. Finfrock, D.M. Meira, G. King, G. Gao, W. Xu, D.A. Cullen, H. Zhou, Y. Han, D.E. Perea, C.L. Muhich, H. Wang, Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst, Nat. Nanotechnol. 17(7) (2022) 759-767.
[13] Z.Y. Wu, Y.H. Song, H.C. Guo, F.T. Xie, Y.T. Cong, M. Kuang, J.P. Yang, Tandem catalysis in electrocatalytic nitrate reduction: unlocking efficiency and mechanism, Interdiscip. Mater. 3(2) (2024) 245-269.
[14] L. Liu, S.J. Zheng, H. Chen, J.M. Cai, S.Q. Zang, Tandem nitrate-to-ammonia conversion on atomically precise silver nanocluster/MXene electrocatalyst, Angew. Chem. Int. Ed 63(8) (2024) e202316910.
[15] T.H. Ding, M.L. Wang, F.J. Wu, B. Song, K. Lu, H. Zhang, Recent advances in electrocatalytic nitrate reduction: strategies to promote ammonia synthesis, ACS Appl. Energy Mater. (2024). https://doi.org/10.1021/acsaem.3c02892.
[16] K. Dong, Y.C. Yao, H.B. Li, H. Li, S.J. Sun, X. He, Y. Wang, Y.S. Luo, D.D. Zheng, Q. Liu, Q. Li, D.W. Ma, X.P. Sun, B. Tang, H₂O₂-mediated electrosynthesis of nitrate from air, Nat. Synth. 3(2024) 763-773.
[17] Y.Y. Wan, Y. Zhang, N.N. Zhang, Z.Y. Zhang, K. Chu, Single-atom Zn on MnO₂ for selective nitrite electrolysis to ammonia, Chem. Eng. J. 481(2024) 148734.
[18] Z. Zhang, A. Niu, Y. Lv, H. Guo, J.S. Chen, Q. Liu, K. Dong, X. Sun, T. Li, NbC nanoparticles decorated carbon nanofibers as highly active and robust heterostructural electrocatalysts for ammonia synthesis, Angew. Chem. Int. Ed 63(30) (2024) e202406441.
[19] X.Y. Fan, C.Z. Liu, Z.X. Li, Z.W. Cai, L. Ouyang, Z.R. Li, X. He, Y.S. Luo, D.D. Zheng, S.J. Sun, Y. Wang, B.W. Ying, Q. Liu, A. Farouk, M.S. Hamdy, F. Gong, X.P. Sun, Y.Y. Zheng, Pd-doped Co₃ O₄ nanoarray for efficient eight-electron nitrate electrocatalytic reduction to ammonia synthesis, Small 19(42) (2023) e2303424.
[20] Y.T. Wang, W. Zhou, R.R. Jia, Y.F. Yu, B. Zhang, Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia, Angew. Chem. Int. Ed 59(13) (2020) 5350-5354.
[21] R.R. Jia, Y.T. Wang, C.H. Wang, Y.F. Ling, Y.F. Yu, B. Zhang, Boosting selective nitrate electroreduction to ammonium by constructing oxygen vacancies in TiO₂, ACS Catal. 10(6) (2020) 3533-3540.
[22] Y.T. Wang, C.H. Wang, M.Y. Li, Y.F. Yu, B. Zhang, Nitrate electroreduction: mechanism insight, in situ characterization, performance evaluation, and challenges, Chem. Soc. Rev. 50(12) (2021) 6720-6733.
[23] B. Min, Q. Gao, Z.H. Yan, X. Han, K. Hosmer, A. Campbell, H.Y. Zhu, Powering the remediation of the nitrogen cycle: progress and perspectives of electrochemical nitrate reduction, Ind. Eng. Chem. Res. 60(41) (2021) 14635-14650.
[24] J.A. Bennett, K. Wilson, A.F. Lee, Catalytic applications of waste derived materials, J. Mater. Chem. A 4(10) (2016) 3617-3637.
[25] Z. Zhang, T. Wang, J. Song Chen, K. Dong, S. Sun, Y. Luo, H. Guo, X. Sun, T. Li, Cr3C₂ nanoparticles decorated carbon nanofibers for efficient nitrate reduction to ammonia at ambient conditions, J. Colloid Interface Sci. 648(2023) 693-700.
[26] P.J. Hu, X.Q. Zhang, M. Xu, Y.X. Lv, H.R. Guo, J.S. Chen, X.Y. Ye, H.H. Xian, X.P. Sun, T.S. Li, In-situ exsolution of FeCo nanoparticles over perovskite oxides for efficient electrocatalytic nitrate reduction to ammonia via localized electrons, Appl. Catal. B Environ. Energy 357(2024) 124267.
[27] Z. Tao, H. Yin, Y. Lv, H. Guo, J.S. Chen, X. Ye, H. Xian, S. Sun, T. Li, Crystalline modulation of zirconia for efficient nitrate reduction to ammonia under ambient conditions, Chem. Commun. 60(42) (2024) 5554-5557.
[28] T. Xie, X. He, L. He, K. Dong, Y.C. Yao, Z.W. Cai, X.W. Liu, X.Y. Fan, T.Y. Li, D.D. Zheng, S.J. Sun, L.M. Li, W. Chu, A. Farouk, M.S. Hamdy, C.G. Xu, Q.Q. Kong, X.P. Sun, CoSe₂ nanowire array enabled highly efficient electrocatalytic reduction of nitrate for ammonia synthesis, Chin. Chem. Lett. 35(11) (2024) 110005.
[29] J. Liang, Z.X. Li, L.C. Zhang, X. He, Y.S. Luo, D.D. Zheng, Y. Wang, T.S. Li, H. Yan, B.W. Ying, S.J. Sun, Q. Liu, M.S. Hamdy, B. Tang, X.P. Sun, Advances in ammonia electrosynthesis from ambient nitrate/nitrite reduction, Chem 9(7) (2023) 1768-1827.
[30] H.R. Zhang, H.J. Wang, X.Q. Cao, M.S. Chen, Y.L. Liu, Y.T. Zhou, M. Huang, L. Xia, Y. Wang, T.S. Li, D.D. Zheng, Y.S. Luo, S.J. Sun, X. Zhao, X.P. Sun, Unveiling cutting-edge developments in electrocatalytic nitrate-to-ammonia conversion, Adv. Mater. 36(16) (2024) e2312746.
[31] L. Qi, Z.G. Sun, Q. Tang, J. Wang, T.Z. Huang, C.Z. Sun, F. Gao, C.J. Tang, L. Dong, Getting insight into the effect of CuO on red mud for the selective catalytic reduction of NO by NH₃, J. Hazard Mater. 396(2020) 122459.
[32] S.Q. Zhang, C. Zhang, Q. Wang, W.S. Ahn, Co- and Mn-coimpregnated ZSM-5 prepared from recycled industrial solid wastes for low-temperature NH₃-SCR, Ind. Eng. Chem. Res. 58(51) (2019) 22857-22865.
[33] Y.T. Xu, K.C. Ren, Z.M. Tao, D.K. Sam, E.L. Feng, X. Wang, G.M. Zhang, J.C. Wu, Y. Cao, A new catalyst based on disposed red mud for the efficient electrochemical reduction of nitrate-to-ammonia, Green Chem. 25(2) (2023) 589-595.
[34] Y.T. Xu, M.Y. Xie, H.Q. Zhong, Y. Cao, In situ clustering of single-atom copper precatalysts in a metal-organic framework for efficient electrocatalytic nitrate-to-ammonia reduction, ACS Catal. 12(14) (2022) 8698-8706.

High-performance red mud as an electrocatalyst for nitrate reduction toward ammonia synthesis

High-performance red mud as an electrocatalyst for nitrate reduction toward ammonia synthesis

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Shuaishuai Zhang, Xinan Sun, Qingwen Luo, Lin Chi, Peng Sun, Lianke Zhang. The Ce-modified biochar for efficient removal of methylene blue dye: Kinetics, isotherms and reusability studies[J]. 中国化学工程学报, 2025, 77(1): 57-65.
[2]	Hongmei Wu, Xinyu Liu, Yu Guo. Preparation of a zeolite-palladium composite membrane for hydrogen separation: Influence of zeolite film on membrane stability[J]. 中国化学工程学报, 2024, 72(8): 44-52.
[3]	Yumiao Lu, Weilu Ding, Kun Li, Yanlei Wang, Bobo Cao, Ruirui He, Hongyan He. Direct observation of ordered-disordered structural transition of MoS₂-confined ionic liquids[J]. 中国化学工程学报, 2024, 72(8): 126-132.
[4]	Zhendong Wang, Bofeng Zhang, Guozhu Liu, Xiangwen Zhang. Thermal stable Pt clusters anchored by K/TiO₂-Al₂O₃ for efficient cycloalkane dehydrogenation[J]. 中国化学工程学报, 2024, 72(8): 187-198.
[5]	Bingning Wang, Xianzhe Wang, Song Yang, Chao Yang, Huiling Fan, Ju Shangguan. Research progress on catalysts for organic sulfur hydrolysis: Review of activity and stability[J]. 中国化学工程学报, 2024, 71(7): 203-216.
[6]	Junyang Li, Roberta Campardelli, Giuseppe Firpo, Jingtao Zhang, Patrizia Perego. Oil-in-water nanoemulsions loaded with lycopene extracts encapsulated by spray drying: Formulation, characterization and optimization[J]. 中国化学工程学报, 2024, 70(6): 73-81.
[7]	Xiaona Liu, Baohua Zhao, Yanyun Hu, Luyue Huang, Jingxiang Ma, Shuqiao Xu, Zhonglin Xia, Xiaoying Ma, Shuangchen Ma. Enhancing capacitive deionization performance and cyclic stability of nitrogen-doped activated carbon by the electro-oxidation of anode materials[J]. 中国化学工程学报, 2024, 69(5): 23-33.
[8]	Yuhang Wei, Qingpeng Zhu, Weiwei Xie, Xinyue Wang, Song Li, Zhiming Chen. Biocatalytic enhancement of laccase immobilized on ZnFe₂O₄ nanoparticles and its application for degradation of textile dyes[J]. 中国化学工程学报, 2024, 68(4): 216-223.
[9]	Yuan Meng, Wanli Tan, Shuang Lv, Fang Liu, Jindun Xu, Xuejiao Ma, Jia Huang. Enhanced electrochemical nitrate removal from groundwater by simply calcined Ti nanopores with modified surface characters[J]. 中国化学工程学报, 2024, 75(11): 74-85.
[10]	Chunjin Zhang, Xue Yao, Linlin Chen, Hua Tang, Siming Chen. Efficient and eco-friendly carbon dioxide capture with metal phosphate catalysts in monoethanolamine solutions[J]. 中国化学工程学报, 2024, 75(11): 121-130.
[11]	Xiaojing Liu, Ruohan Zhao, Hao Zhao, Zhimiao Wang, Fang Li, Wei Xue, Yanji Wang. Enhanced stability of nitrogen-doped carbon-supported palladium catalyst for oxidative carbonylation of phenol[J]. 中国化学工程学报, 2024, 65(1): 19-28.
[12]	Fangren Qian, Lishan Peng, Yujuan Zhuang, Lei Liu, Qingjun Chen. Direct atomic-level insight into oxygen reduction reaction on size-dependent Pt-based electrocatalysts from density functional theory calculations[J]. 中国化学工程学报, 2023, 61(9): 140-146.
[13]	Jianfeng Cheng, Meixuan Li, Yutong Wang, Jiexiang Li, Jiawei Wen, Chunxia Wang, Guoyong Huang. Effects of Al and Co doping on the structural stability and high temperature cycling performance of LiNi_0.5Mn_1.5O₄ spinel cathode materials[J]. 中国化学工程学报, 2023, 61(9): 201-209.
[14]	Peipei Ai, Huiqing Jin, Jie Li, Xiaodong Wang, Wei Huang. Ultra-stable Cu-based catalyst for dimethyl oxalate hydrogenation to ethylene glycol[J]. 中国化学工程学报, 2023, 60(8): 186-193.
[15]	Bingxiao Feng, Lining Hao, Chaoting Deng, Jiaqiang Wang, Hongbing Song, Meng Xiao, Tingting Huang, Quanhong Zhu, Hengjun Gai. A highly hydrothermal stable copper-based catalyst for catalytic wet air oxidation of m-cresol in coal chemical wastewater[J]. 中国化学工程学报, 2023, 57(5): 338-348.