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
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–1cat. 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.