Zhao Shuya, Zheng Zhiqiang, Qi Lu, Xue Yurui, Li Yuliang
Science Center for Material Creation and Energy Conversion, Institute of Frontier and Interdisciplinary Science, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, P. R. China.
Small. 2022 Apr;18(13):e2107136. doi: 10.1002/smll.202107136. Epub 2022 Feb 4.
The intrinsic catalytic activity and active sites of the catalyst originate from the interface efficient charge transfer. A 2D graphdiyne (GDY) layer grown on the surface of zeolitic imidazolate framework nanocubes (ZIFNC@GDY) forms a novel structure of a perfect "donor-bridge-acceptor" interface, in which the ZIFNC and GDY act as electron donor and acceptor, respectively, linked by the sp-C-Co and sp-C-N bonds as bridges. Importantly, the as-prepared catalyst exhibits intrinsically high reactivity for ammonia production through the nitrate reduction reaction (NtRR) in neutral aqueous solutions at ambient pressures and temperatures. The NtRR performance of the as-prepared electrocatalyst is confirmed by the high NH yield rate (Y ) of 0.40 ± 0.02 mmol h cm at potential of -0.745V versus RHE and Faradaic efficiency (FE) of 98.51 ± 0.75%, as well as the excellent stability. We show that such unique interfacial structures can accelerate the efficient electron transfers between the zeolitic imidazolate framework nanocubes (ZIFNC) core and GDY shell, enrich the electron density on the GDY surface, and thereby promote fast redox switching, creating more active sites, and improving the catalytic performances.
催化剂的本征催化活性和活性位点源于界面高效电荷转移。生长在沸石咪唑酯骨架纳米立方体（ZIFNC@GDY）表面的二维石墨炔（GDY）层形成了一种新型的完美“供体-桥-受体”界面结构，其中ZIFNC和GDY分别作为电子供体和受体，通过sp-C-Co和sp-C-N键作为桥连接。重要的是，所制备的催化剂在环境压力和温度下的中性水溶液中通过硝酸盐还原反应（NtRR）表现出本征的高氨生产反应活性。所制备的电催化剂的NtRR性能通过在相对于可逆氢电极（RHE）为-0.745V的电位下0.40±0.02 mmol h⁻¹ cm⁻²的高NH₃产率（Y）、98.51±0.75%的法拉第效率（FE）以及优异的稳定性得到证实。我们表明，这种独特的界面结构可以加速沸石咪唑酯骨架纳米立方体（ZIFNC）核与GDY壳之间的高效电子转移，富集GDY表面的电子密度，从而促进快速氧化还原转换，产生更多活性位点，并提高催化性能。
