Unveiling the size effect of nitrogen-doped carbon-supported copper-based catalysts on nitrate-to-ammonia electroreduction

Ran Li; Taotao Gao; Wenxi Qiu; Minghao Xie; Zhaoyu Jin; Panpan Li

doi:10.1007/s12274-023-6094-z

Nano Research 2024, 17(4): 2438-2443 https://doi.org/10.1007/s12274-023-6094-z

Research Article | Issue | Published: 18 September 2023

Unveiling the size effect of nitrogen-doped carbon-supported copper-based catalysts on nitrate-to-ammonia electroreduction

Show Author's Information Hide Author's Information Ran Li^{¹^,²}, Taotao Gao^²(

), Wenxi Qiu^¹, Minghao Xie^³, Zhaoyu Jin^⁴, Panpan Li^¹(

)

1College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China

2Institute for Advanced Study, Chengdu University, Chengdu 610106, China

3Materials Science and Engineering Program and Walker Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, USA

4Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China

Keywords:

size effect, ammonia electrosynthesis, nitrate electroreduction, single-cluster catalyst

Topics:

Catalyst activity Electrocatalysis Electrolytic reduction

Cite this article:

Li R, Gao T, Qiu W, et al. Unveiling the size effect of nitrogen-doped carbon-supported copper-based catalysts on nitrate-to-ammonia electroreduction. Nano Research, 2024, 17(4): 2438-2443. https://doi.org/10.1007/s12274-023-6094-z

Download citation

EndNote(RIS)

BibTeX

834

Views

135

Downloads

Citations

Crossref

WoS

Scopus

CSCD

Abstract Full text Electronic supplementary material About this article

Abstract

The electrocatalytic nitrate reduction reaction (NitRR) represents a promising approach toward achieving economically and environmentally sustainable ammonia. However, it remains a challenge to regulate the size effect of electrocatalysts to optimize the catalytic activity and ammonia selectivity. Herein, the Cu-based catalysts were tailored at the atomic level to exhibit a size gradient ranging from single-atom catalysts (SACs, 0.15–0.35 nm) to single-cluster catalysts (SCCs, 1.0–2.8 nm) and nanoparticles (NPs, 20–30 nm), with the aim of studying the size effect for the NO₃⁻-to-NH₃ reduction reaction. Especially, the Cu SCCs exhibit enhanced metal–substrate and metal–metal interactions by taking advantageous features of Cu SACs and Cu NPs. Thus, Cu SCCs achieve exceptional electrocatalytic performance for the NitRR with a maximum Faradaic efficiency of ca. 96% and the largest yield rate of ca. 1.99 mg $_{{N H}_{3}}$ ·h⁻¹·cm⁻² at −0.5 V vs. reversible hydrogen electrode (RHE). The theoretical calculation further reveals the size effect and coordination environment on the high catalytic activity and selectivity for the NitRR. This work provides a promising various size-controlled design strategy for aerogel-based catalysts effectively applied in various electrocatalytic reactions.

Full text

Abstract

Full text

Outline

Electronic supplementary material

About this article

Unveiling the size effect of nitrogen-doped carbon-supported copper-based catalysts on nitrate-to-ammonia electroreduction

Show Author's information Hide Author's Information Ran Li^{¹^,²}, Taotao Gao^²(

), Wenxi Qiu^¹, Minghao Xie^³, Zhaoyu Jin^⁴, Panpan Li^¹(

)

1College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China

2Institute for Advanced Study, Chengdu University, Chengdu 610106, China

3Materials Science and Engineering Program and Walker Department of Mechanical Engineering, The University of Texas at Austin, Austin, Texas 78712, USA

4Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China

Abstract

Keywords: size effect, ammonia electrosynthesis, nitrate electroreduction, single-cluster catalyst

References(50)

[1]

Jung, W.; Hwang, Y. J. Material strategies in the electrochemical nitrate reduction reaction to ammonia production. Mater. Chem. Front. 2021, 5, 6803–6823.

DOI Google Scholar

[2]

Liang, J.; Liu, Q.; Alshehri, A. A.; Sun, X. P. Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis. Nano Res. Energy 2022, 1, e9120010.

DOI Google Scholar

[3]

Canfield, D. E.; Glazer, A. N.; Falkowski, P. G. The evolution and future of earth’s nitrogen cycle. Science 2010, 330, 192–196.

DOI Google Scholar

[4]

Erisman, J. W.; Sutton, M. A.; Galloway, J.; Klimont, Z.; Winiwarter, W. How a century of ammonia synthesis changed the world. Nat. Geosci. 2008, 1, 636–639.

DOI Google Scholar

[5]

Zhang, G. K.; Li, X. T.; Chen, K.; Guo, Y. L.; Ma, D. W.; Chu, K. Tandem electrocatalytic nitrate reduction to ammonia on MBenes. Angew. Chem., Int. Ed. 2023, 62, e202300054.

DOI Google Scholar

[6]

Zhang, N. N.; Zhang, G. K.; Shen, P.; Zhang, H.; Ma, D. W.; Chu, K. Lewis acid Fe–V pairs promote nitrate electroreduction to ammonia. Adv. Funct. Mater. 2023, 33, 2211537.

DOI Google Scholar

[7]

Duca, M.; Koper, M. T. M. Powering denitrification: The perspectives of electrocatalytic nitrate reduction. Energy Environ. Sci. 2012, 5, 9726–9742.

DOI Google Scholar

[8]

Stein, L. Y.; Klotz, M. G. The nitrogen cycle. Curr. Biol. 2016, 26, R94–R98.

DOI Google Scholar

[9]

Garcia-Segura, S.; Lanzarini-Lopes, M.; Hristovski, K.; Westerhoff, P. Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications. Appl. Catal. B: Environ. 2018, 236, 546–568.

DOI Google Scholar

[10]

Gruber, N.; Galloway, J. N. An earth-system perspective of the global nitrogen cycle. Nature 2008, 451, 293–296.

DOI Google Scholar

[11]

Xu, H.; Ma, Y. Y.; Chen, J.; Zhang, W. X.; Yang, J. P. Electrocatalytic reduction of nitrate-a step towards—A sustainable nitrogen cycle. Chem. Soc. Rev. 2022, 51, 2710–2758.

DOI Google Scholar

[12]

Xie, M. H.; Zhang, B. W.; Jin, Z. Y.; Li, P. P.; Yu, G. H. Atomically reconstructed palladium metallene by intercalation-induced lattice expansion and amorphization for highly efficient electrocatalysis. ACS Nano 2022, 16, 13715–13727.

DOI Google Scholar

[13]

Li, X. T.; Shen, P.; Li, X. C.; Ma, D. W.; Chu, K. Sub-nm RuO_x clusters on Pd metallene for synergistically enhanced nitrate electroreduction to ammonia. ACS Nano 2023, 17, 1081–1090.

DOI Google Scholar

[14]

Liu, Y. T.; Liu, K.; Wang, P. F.; Jin, Z. Y.; Li, P. P. Electrocatalytic upcycling of nitrogenous wastes into green ammonia: Advances and perspectives on materials innovation. Carb. Neutrality 2023, 2, 14.

DOI Google Scholar

[15]

Li, R.; Gao, T. T.; Wang, P. F.; Qiu, W. X.; Liu, K.; Liu, Y. T.; Jin, Z. Y.; Li, P. P. The origin of selective nitrate-to-ammonia electroreduction on metal-free nitrogen-doped carbon aerogel catalysts. Appl. Catal. B: Environ. 2023, 331, 122677.

DOI Google Scholar

[16]

Li, P. P.; Li, R.; Liu, Y. T.; Xie, M. H.; Jin, Z. Y.; Yu, G. H. Pulsed nitrate-to-ammonia electroreduction facilitated by tandem catalysis of nitrite intermediates. J. Am. Chem. Soc. 2023, 145, 6471–6479.

DOI Google Scholar

[17]

Li, P. P.; Jin, Z. Y.; Fang, Z. W.; Yu, G. H. A surface-strained and geometry-tailored nanoreactor that promotes ammonia electrosynthesis. Angew. Chem., Int. Ed. 2020, 59, 22610–22616.

DOI Google Scholar

[18]

Gao, T. T.; Yu, S. M.; Chen, Y. T.; Li, X. Q.; Tang, X. M.; Wu, S. W.; He, B.; Lan, H.; Li, S. L.; Yue, Q. et al. Regulating the thickness of the carbon coating layer in iron/carbon heterostructures to enhance the catalytic performance for oxygen evolution reaction. J. Colloid Interface Sci. 2023, 642, 120–128.

DOI Google Scholar

[19]

Gao, T. T.; Tang, X. M.; Li, X. Q.; Lan, H.; Yu, S. M.; Wu, S. W.; Yue, Q.; Xiao, D. Surface reconstructing hierarchical structures as robust sulfion oxidation catalysts to produce hydrogen with ultralow energy consumption. Inorg. Chem. Front. 2023, 10, 1447–1456.

DOI Google Scholar

[20]

Qiu, W. X.; Chen, X. J.; Liu, Y. T.; Xiao, D.; Wang, P. F.; Li, R.; Liu, K.; Jin, Z. Y.; Li, P. P. Confining intermediates within a catalytic nanoreactor facilitates nitrate-to-ammonia electrosynthesis. Appl. Catal. B: Environ. 2022, 315, 121548.

DOI Google Scholar

[21]

Mi, L. R.; Huo, Q. H.; Cao, J. Y.; Chen, X. B.; Yang, H. P.; Hu, Q.; He, C. X. Achieving synchronization of electrochemical production of ammonia from nitrate and ammonia capture by constructing a “two-in-one” flow cell electrolyzer. Adv. Energy Mater. 2022, 12, 2202247.

DOI Google Scholar

[22]

Li, L. L.; Hasan, I. M. U.; Farwa; He, R. N.; Peng, L. W.; Xu, N. N.; Niazi, N. K.; Zhang, J. N.; Qiao, J. L. Copper as a single metal atom based photo-, electro-, and photoelectrochemical catalyst decorated on carbon nitride surface for efficient CO₂ reduction: A review. Nano Res. Energy 2022, 1, e9120015.

DOI Google Scholar

[23]

Liu, Y. T.; Qiu, W. X.; Wang, P. F.; Li, R.; Liu, K.; Omer, K. M.; Jin, Z. Y.; Li, P. P. Pyridine-N-rich Cu single-atom catalyst boosts nitrate electroreduction to ammonia. Appl. Catal. B: Environ 2024, 340, 123228.

DOI Google Scholar

[24]

Liu, H. M.; Lang, X. Y.; Zhu, C.; Timoshenko, J.; Rüscher, M.; Bai, L. C.; Guijarro, N.; Yin, H. B.; Peng, Y.; Li, J. H. et al. Efficient electrochemical nitrate reduction to ammonia with copper-supported rhodium cluster and single-atom catalysts. Angew. Chem., Int. Ed. 2022, 61, e202202556.

DOI Google Scholar

[25]

Qiu, W. X.; Xie, M. H.; Wang, P. F.; Gao, T. T.; Li, R.; Xiao, D.; Jin, Z. Y.; Li, P. P. Size-defined Ru nanoclusters supported by TiO₂ nanotubes enable low-concentration nitrate electroreduction to ammonia with suppressed hydrogen evolution. Small 2023, 19, 2300437.

DOI Google Scholar

[26]

Niu, H.; Zhang, Z. F.; Wang, X. T.; Wan, X. H.; Shao, C.; Guo, Y. Z. Theoretical insights into the mechanism of selective nitrate-to-ammonia electroreduction on single-atom catalysts. Adv. Funct. Mater. 2021, 31, 2008533.

DOI Google Scholar

[27]

Wu, Z. Y.; Karamad, M.; Yong, X.; Huang, Q. Z.; Cullen, D. A.; Zhu, P.; Xia, C.; Xiao, Q. F.; Shakouri, M.; Chen, F. Y. et al. Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst. Nat. Commun. 2021, 12, 2870.

DOI Google Scholar

[28]

Cai, J. M.; Wei, Y. Y.; Cao, A.; Huang, J. J.; Jiang, Z.; Lu, S. Y.; Zang, S. Q. Electrocatalytic nitrate-to-ammonia conversion with ~ 100% Faradaic efficiency via single-atom alloying. Appl. Catal. B: Environ. 2022, 316, 121683.

DOI Google Scholar

[29]

Li, P. P.; Jin, Z. Y.; Fang, Z. W.; Yu, G. H. A single-site iron catalyst with preoccupied active centers that achieves selective ammonia electrosynthesis from nitrate. Energy Environ. Sci. 2021, 14, 3522–3531.

DOI Google Scholar

[30]

Jin, Z. Y.; Li, P. P.; Fang, Z. W.; Yu, G. H. Emerging electrochemical techniques for probing site behavior in single-atom electrocatalysts. Acc. Chem. Res. 2022, 55, 759–769.

DOI Google Scholar

[31]

Chen, K.; Ma, Z. Y.; Li, X. C.; Kang, J. L.; Ma, D. W.; Chu, K. Single-atom Bi alloyed Pd metallene for nitrate electroreduction to ammonia. Adv. Funct. Mater. 2023, 33, 2209890.

DOI Google Scholar

[32]

Chen, K.; Zhang, G. K.; Li, X. T.; Zhao, X. L.; Chu, K. Electrochemical NO reduction to NH₃ on Cu single atom catalyst. Nano Res. 2023, 16, 5857–5863.

DOI Google Scholar

[33]

Gao, T. T.; Qiu, L.; Xie, M. H.; Jin, Z. Y.; Li, P. P.; Yu, G. H. Defect-stabilized and oxygen-coordinated iron single-atom sites facilitate hydrogen peroxide electrosynthesis. Mater. Horiz., in press, https://doi.org/10.1039/D3MH00882G.

[34]

Yang, J.; Qi, H. F.; Li, A. Q.; Liu, X. Y.; Yang, X. F.; Zhang, S. X.; Zhao, Q.; Jiang, Q. K.; Su, Y.; Zhang, L. L. et al. Potential-driven restructuring of Cu single atoms to nanoparticles for boosting the electrochemical reduction of nitrate to ammonia. J. Am. Chem. Soc. 2022, 144, 12062–12071.

DOI Google Scholar

[35]

Xu, Y. T.; Xie, M. Y.; Zhong, H. Q.; Cao, Y. In situ clustering of single-atom copper precatalysts in a metal-organic framework for efficient electrocatalytic nitrate-to-ammonia reduction. ACS Catal. 2022, 12, 8698–8706.

DOI Google Scholar

[36]

Gao, T. T.; Tang, X. M.; Li, X. Q.; Wu, S. W.; Yu, S. M.; Li, P. P.; Xiao, D.; Jin, Z. Y. Understanding the atomic and defective interface effect on ruthenium clusters for the hydrogen evolution reaction. ACS Catal. 2023, 13, 49–59.

DOI Google Scholar

[37]

Qi, Y. Y.; Fenes, E.; Ma, H. F.; Wang, Y. L.; Rout, K. R.; Fuglerud, T.; Piccinini, M.; Chen, D. Cluster-size-dependent interaction between ethylene and CuCl2 clusters supported via γ-alumina. J. Phys. Chem. C 2020, 124, 10430–10440.

DOI Google Scholar

[38]

Xing, D. H.; Xu, C. Q.; Wang, Y. G.; Li, J. Heterogeneous single-cluster catalysts for selective semihydrogenation of acetylene with graphdiyne-supported triatomic clusters. J. Phys. Chem. C 2019, 123, 10494–10500.

DOI Google Scholar

[39]

Liu, J. C.; Xiao, H.; Zhao, X. K.; Zhang, N. N.; Liu, Y.; Xing, D. H.; Yu, X. H.; Hu, H. S.; Li, J. Computational prediction of graphdiyne-supported three-atom single-cluster catalysts. CCS Chem. 2023, 5, 152–163.

DOI Google Scholar

[40]

Jin, Z. Y.; Bard, A. J. Surface interrogation of electrodeposited MnO_x and CaMnO₃ perovskites by scanning electrochemical microscopy: Probing active sites and kinetics for the oxygen evolution reaction. Angew. Chem. 2021, 133, 807–812.

DOI Google Scholar

[41]

Li, P. P.; Jin, Z. Y.; Qian, Y. M.; Fang, Z. W.; Xiao, D.; Yu, G. H. Supramolecular confinement of single Cu atoms in hydrogel frameworks for oxygen reduction electrocatalysis with high atom utilization. Mater. Today 2020, 35, 78–86.

DOI Google Scholar

[42]

Li, P. P.; Jin, Z. Y.; Qian, Y. M.; Fang, Z. W.; Xiao, D.; Yu, G. H. Probing enhanced site activity of Co-Fe bimetallic subnanoclusters derived from dual cross-linked hydrogels for oxygen electrocatalysis. ACS Energy Lett. 2019, 4, 1793–1802.

DOI Google Scholar

[43]

Xu, H.; Chen, J. L.; Zhang, Z. H.; Hung, C. T.; Yang, J. P.; Li, W. In situ confinement of ultrasmall metal nanoparticles in short mesochannels for durable electrocatalytic nitrate reduction with high efficiency and selectivity. Adv. Mater. 2023, 35, 2207522.

DOI Google Scholar

[44]

Guan, A. X.; Chen, Z.; Quan, Y. L.; Peng, C.; Wang, Z. Q.; Sham, T. K.; Yang, C.; Ji, Y. L.; Qian, L. P.; Xu, X. et al. Boosting CO₂ electroreduction to CH₄ via tuning neighboring single-copper sites. ACS Energy Lett. 2020, 5, 1044–1053.

DOI Google Scholar

[45]

Groothaert, M. H.; van Bokhoven, J. A.; Battiston, A. A.; Weckhuysen, B. M.; Schoonheydt, R. A. Bis(μ-oxo) dicopper in Cu-ZSM-5 and its role in the decomposition of NO: A combined in situ XAFS, UV–Vis–near-IR, and kinetic study. J. Am. Chem. Soc. 2003, 125, 7629–7640.

DOI Google Scholar

[46]

Meng, F. C.; Peng, M.; Chen, Y. L.; Cai, X. B.; Huang, F.; Yang, L. N.; Liu, X.; Li, T.; Wen, X. D.; Wang, N. et al. Defect-rich graphene stabilized atomically dispersed Cu₃ clusters with enhanced oxidase-like activity for antibacterial applications. Appl. Catal. B: Environ. 2022, 301, 120826.

DOI Google Scholar

[47]

Wang, Y. T.; Zhou, W.; Jia, R. R.; Yu, Y. F.; Zhang, B. Unveiling the activity origin of a copper-based electrocatalyst for selective nitrate reduction to ammonia. Angew. Chem., Int. Ed. 2020, 59, 5350–5354.

DOI Google Scholar

[48]

Platzman, I.; Brener, R.; Haick, H.; Tannenbaum, R. Oxidation of polycrystalline copper thin films at ambient conditions. J. Phys. Chem. C 2008, 112, 1101–1108.

DOI Google Scholar

[49]

Zhai, W. J.; Huang, S. H.; Lu, C. B.; Tang, X. N.; Li, L. B.; Huang, B. Y.; Hu, T.; Yuan, K.; Zhuang, X. D.; Chen, Y. W. Simultaneously integrate iron single atom and nanocluster triggered tandem effect for boosting oxygen electroreduction. Small 2022, 18, 2107225.

DOI Google Scholar

[50]

Wang, Q. L.; Cheng, Y. Q.; Tao, H. B.; Liu, Y. H.; Ma, X. H.; Li, D. S.; Yang, H. B.; Liu, B. Long-term stability challenges and opportunities in acidic oxygen evolution electrocatalysis. Angew. Chem., Int. Ed. 2023, 62, e202216645.

DOI Google Scholar

Electronic supplementary material

File

12274_2023_6094_MOESM1_ESM.pdf (2.3 MB)

About this article

Publication history

Acknowledgements

Publication history

Received: 15 June 2023

Revised: 10 August 2023

Accepted: 14 August 2023

Published: 18 September 2023

Issue date: April 2024

Copyright

Acknowledgements

P. P. L. acknowledges the funding support from the National Nature Science Foundation of China (No. 52202372), the Sichuan Science and Technology Program (Nos. 2023NSFSC0436 and 2023NSFSC0089), and the Fundamental Research Funds for the Central Universities (Nos. YJ2021151 and 20826041G4185). T. T. G. acknowledges the Chengdu University new faculty start-up funding (No. 2081920074). The authors would like to thank Xie Han from Shiyanjia Lab (www.shiyanjia.com) for the XPS tests.