Interfacial Reduction Nucleation of Noble Metal Nanodots on Redox-Active Metal-Organic Frameworks for High-Efficiency Electrocatalytic Conversion of Nitrate to Ammonia

Minghang Jiang; Jian Su; Xinmei Song; Pengbo Zhang; Mengfei Zhu; Lina Qin; Zuoxiu Tie; Jing-Lin Zuo; Zhong Jin

doi:10.1021/acs.nanolett.2c00446

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 Mar 23;22(6):2529-2537. doi: 10.1021/acs.nanolett.2c00446. Epub 2022 Mar 10.

Authors

Minghang Jiang^{1

2}, Jian Su¹, Xinmei Song¹, Pengbo Zhang¹, Mengfei Zhu¹, Lina Qin¹, Zuoxiu Tie^{1

2}, Jing-Lin Zuo¹, Zhong Jin^{1

2}

Affiliations

¹ State Key Laboratory of Coordination Chemistry, MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210023, China.
² Suzhou Tierui New Energy Technology Co. Ltd., Suzhou, Jiangsu 215228, China.

PMID: 35266387
DOI: 10.1021/acs.nanolett.2c00446

Abstract

Electrochemically converting nitrate to ammonia is a promising route to realize artificial nitrogen recycling. However, developing highly efficient electrocatalysts is an ongoing challenge. Herein, we report the construction of stable and redox-active zirconium metal-organic frameworks (Zr-MOFs) based on Zr₆ nanoclusters and redox-reversible tetrathiafulvalene (TTF) derivatives as inorganic nodes and organic linkers, respectively. The redox-active Zr-MOF can facilitate the in situ reduction of noble metal precursors free of external reductants and realize the uniform nucleation of noble metal nanodots (NDs) on Zr-MOF, achieving the preparation of M-NDs/Zr-MOF (M = Pd, Ag, or Au). The highly porous Zr-MOF with good conductivity can facilitate the mass transfer process. Among the M-NDs/Zr-MOF catalysts, Pd-NDs/Zr-MOF exhibits the highest electrocatalytic activity, delivering a NH₃ yield of 287.31 mmol·h^-1·g^-1_cat. and a Faradaic efficiency of 58.1%. The proposed interfacial reduction nucleation strategy for anchoring M NDs on Zr-MOFs can be applied to other challenging energy conversion reactions.

Keywords: Electrochemical nitrate reduction; Interfacial reduction nucleation; Noble metal nanodots; Redox-active metal−organic frameworks.