Sim Howard Yi Fan, Chen Jaslyn Ru Ting, Koh Charlynn Sher Lin, Lee Hiang Kwee, Han Xuemei, Phan-Quang Gia Chuong, Pang Jing Yi, Lay Chee Leng, Pedireddy Srikanth, Phang In Yee, Yeow Edwin Kok Lee, Ling Xing Yi
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
Institute of Materials Research and Engineering, Agency for Science, Technology and Research (A*STAR), 2 Fusionopolis Way, Innovis, #08-03, Singapore, 138634, Singapore.
Angew Chem Int Ed Engl. 2020 Sep 21;59(39):16997-17003. doi: 10.1002/anie.202006071. Epub 2020 Jul 27.
The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst-H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg h under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst-N interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-N interaction is key to enable strong N adsorption over H atom.
电化学氮还原反应（NRR）为氨的生产提供了一种可持续的解决方案，但由于优先形成催化剂 - 氢以及随之而来的析氢反应（HER），其反应性能较差。现在，使用沸石咪唑框架（ZIF）对Pt/Au电催化剂的d带结构进行电子修饰，在环境条件下实现了>44%的法拉第效率（FE）和>161 μg mg⁻¹ h⁻¹的高氨产率。该策略降低了电催化剂的d带位置以减弱氢吸附，同时通过促进催化剂 - 氮相互作用产生缺电子位点以动力学方式驱动NRR。电催化剂上的ZIF涂层兼作疏水层以抑制HER，与没有ZIF的情况（约1%）相比，FE进一步提高了>44倍。Pt/Au - 氮相互作用是实现氮比氢原子更强吸附的关键。
