Zou Yingying, Yan Yuechen, Xue Qingsong, Zhang Chaoqi, Bao Tong, Zhang Xinchan, Yuan Ling, Qiao Sicong, Song Li, Zou Jin, Yu Chengzhong, Liu Chao
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200241, P. R. China.
National Synchrotron Radiation Laboratory, Key Laboratory of Precision and Intelligent Chemistry, School of Nuclear Science and Technology, University of Science and Technology of China, Hefei, 230029, P. R. China.
Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202409799. doi: 10.1002/anie.202409799. Epub 2024 Sep 10.
Electrocatalytic nitrate reduction reaction (NO RR) is an important route for sustainable NH synthesis and environmental remediation. Metal-organic frameworks (MOFs) are one family of promising NO RR electrocatalysts, however, there is plenty of room to improve in their performance, calling for new design principles. Herein, a MOF-on-MOF heterostructured electrocatalyst with interfacial dual active sites and build-in electric field is fabricated for efficient NO RR to NH production. By growing Co-HHTP (HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) nanorods on Ni-BDC (BDC=1,4-benzenedicarboxylate) nanosheets, experimental and theoretical investigations demonstrate the formation of Ni-O-Co bonds at the interface of MOF-on-MOF heterostructure, leading to dual active sites tailed for NO RR. The Ni sites facilitate the adsorption and activation of NO , while the Co sites boost the HO decomposition to supply active hydrogen (H) for N-containing intermediates hydrogenation on adjacent Ni sites, cooperatively reducing the energy barriers of NO RR process. Together with the accelerated electron transfer enabled by built-in electric field, remarkable NO RR performance is achieved with an NH yield rate of 11.46 mg h cm and a Faradaic efficiency of 98.4 %, outperforming most reported MOF-based electrocatalysts. This work provides new insights into the design of high-performance NO RR electrocatalysts.
电催化硝酸盐还原反应（NO RR）是实现可持续氨合成和环境修复的重要途径。金属有机框架（MOF）是一类很有前景的NO RR电催化剂，然而，其性能仍有很大的提升空间，需要新的设计原则。在此，制备了一种具有界面双活性位点和内置电场的MOF-on-MOF异质结构电催化剂，用于高效的NO RR制氨。通过在Ni-BDC（BDC = 1,4-苯二甲酸）纳米片上生长Co-HHTP（HHTP = 2,3,6,7,10,11-六羟基三亚苯）纳米棒，实验和理论研究表明在MOF-on-MOF异质结构界面形成了Ni-O-Co键，从而产生了针对NO RR的双活性位点。Ni位点促进NO的吸附和活化，而Co位点促进H2O分解，为相邻Ni位点上含氮中间体的氢化提供活性氢（H*），协同降低NO RR过程的能垒。再加上内置电场加速电子转移，实现了卓越的NO RR性能，氨产率为11.46 mg h−1 cm−2，法拉第效率为98.4%，优于大多数报道的基于MOF的电催化剂。这项工作为高性能NO RR电催化剂的设计提供了新的见解。
