Insights into the Origin of Activity Enhancement Via Tuning Electronic Structure of CuO Towards Electrocatalytic Ammonia Synthesis

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2024 May 25

PMID 38792124

Authors

Meimei Kou

Ying Yuan

Ruili Zhao

Youkui Wang

Jiamin Zhao

Qing Yuan

Jinsheng Zhao

Affiliations

Soon will be listed here.

Abstract

The insight of the activity phase and reaction mechanism is vital for developing high-performance ammonia synthesis electrocatalysts. In this study, the origin of the electronic-dependent activity for the model CuO catalyst toward ammonia electrosynthesis with nitrate was probed. The modulation of the electronic state and oxygen vacancy content of CuO was realized by doping with halogen elements (Cl, Br, I). The electrocatalytic experiments showed that the activity of the ammonia production depends strongly on the electronic states in CuO. With increased electronic state defects in CuO, the ammonia synthesis performance increased first and then decreased. The CuO/Br with electronic defects in the middle showed the highest ammonia yield of 11.4 g h g at -1.0 V (vs. RHE), indicating that the pattern of change in optimal ammonia activity is consistent with the phenomenon of volcano curves in reaction chemistry. This work highlights a promising route for designing NORR to NH catalysts.

References

Aresta M, Dibenedetto A, Angelini A . Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels. technological use of CO2. Chem Rev. 2013; 114(3):1709-42. DOI: 10.1021/cr4002758. View

Jiang M, Su J, Song X, Zhang P, Zhu M, Qin L . Interfacial Reduction Nucleation of Noble Metal Nanodots on Redox-Active Metal-Organic Frameworks for High-Efficiency Electrocatalytic Conversion of Nitrate to Ammonia. Nano Lett. 2022; 22(6):2529-2537. DOI: 10.1021/acs.nanolett.2c00446. View

Fang J, Zheng Q, Lou Y, Zhao K, Hu S, Li G . Ampere-level current density ammonia electrochemical synthesis using CuCo nanosheets simulating nitrite reductase bifunctional nature. Nat Commun. 2022; 13(1):7899. PMC: 9780304. DOI: 10.1038/s41467-022-35533-6. View

Zhang Y, Cao L, Bai G, Lan X . Engineering Single Cu Sites into Covalent Organic Framework for Selective Photocatalytic CO Reduction. Small. 2023; 19(22):e2300035. DOI: 10.1002/smll.202300035. View

Jiang H, Chen G, Savateev O, Xue J, Ding L, Liang Z . Enabled Efficient Ammonia Synthesis and Energy Supply in a Zinc-Nitrate Battery System by Separating Nitrate Reduction Process into Two Stages. Angew Chem Int Ed Engl. 2023; 62(13):e202218717. DOI: 10.1002/anie.202218717. View

Zhu X, Huang H, Zhang H, Zhang Y, Shi P, Qu K . Filling Mesopores of Conductive Metal-Organic Frameworks with Cu Clusters for Selective Nitrate Reduction to Ammonia. ACS Appl Mater Interfaces. 2022; 14(28):32176-32182. DOI: 10.1021/acsami.2c09241. View

Zhou Y, Ganganahalli R, Verma S, Tan H, Yeo B . Production of C -C Acetate Esters via CO Electroreduction in a Membrane Electrode Assembly Cell. Angew Chem Int Ed Engl. 2022; 61(29):e202202859. DOI: 10.1002/anie.202202859. View

Yang J, Liu W, Xu M, Liu X, Qi H, Zhang L . Dynamic Behavior of Single-Atom Catalysts in Electrocatalysis: Identification of Cu-N as an Active Site for the Oxygen Reduction Reaction. J Am Chem Soc. 2021; 143(36):14530-14539. DOI: 10.1021/jacs.1c03788. View

Wang Z, Sun C, Bai X, Wang Z, Yu X, Tong X . Facile Synthesis of Carbon Nanobelts Decorated with Cu and Pd for Nitrate Electroreduction to Ammonia. ACS Appl Mater Interfaces. 2022; 14(27):30969-30978. DOI: 10.1021/acsami.2c09357. View

10.

Li S, Sha X, Gao X, Peng J . Al-Doped Octahedral CuO Nanocrystal for Electrocatalytic CO Reduction to Produce Ethylene. Int J Mol Sci. 2023; 24(16). PMC: 10454826. DOI: 10.3390/ijms241612680. View

11.

Sun D, Li Z, Huang S, Chi J, Zhao S . Efficient mercury removal in chlorine-free flue gas by doping Cl into CuO nanocrystals. J Hazard Mater. 2021; 419:126423. DOI: 10.1016/j.jhazmat.2021.126423. View

12.

Zhang S, Wu J, Zheng M, Jin X, Shen Z, Li Z . Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia. Nat Commun. 2023; 14(1):3634. PMC: 10279643. DOI: 10.1038/s41467-023-39366-9. View

13.

Liu Y, Tu X, Wei X, Wang D, Zhang X, Chen W . C-Bound or O-Bound Surface: Which One Boosts Electrocatalytic Urea Synthesis?. Angew Chem Int Ed Engl. 2023; 62(19):e202300387. DOI: 10.1002/anie.202300387. View

14.

Xu J, Zhang S, Liu H, Liu S, Yuan Y, Meng Y . Breaking Local Charge Symmetry of Iron Single Atoms for Efficient Electrocatalytic Nitrate Reduction to Ammonia. Angew Chem Int Ed Engl. 2023; 62(39):e202308044. DOI: 10.1002/anie.202308044. View

15.

Legare M, Belanger-Chabot G, Dewhurst R, Welz E, Krummenacher I, Engels B . Nitrogen fixation and reduction at boron. Science. 2018; 359(6378):896-900. DOI: 10.1126/science.aaq1684. View

16.

Wang Y, Zhou W, Jia R, Yu Y, Zhang B . Unveiling the Activity Origin of a Copper-based Electrocatalyst for Selective Nitrate Reduction to Ammonia. Angew Chem Int Ed Engl. 2020; 59(13):5350-5354. DOI: 10.1002/anie.201915992. View

17.

Wu Z, Karamad M, Yong X, Huang Q, Cullen D, Zhu P . Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst. Nat Commun. 2021; 12(1):2870. PMC: 8128876. DOI: 10.1038/s41467-021-23115-x. View

18.

Li W, Li K, Ye Y, Zhang S, Liu Y, Wang G . Efficient electrocatalytic nitrogen reduction to ammonia with aqueous silver nanodots. Commun Chem. 2023; 4(1):10. PMC: 9814735. DOI: 10.1038/s42004-021-00449-7. View