Han Lili, Ren Zhouhong, Ou Pengfei, Cheng Hao, Rui Ning, Lin Lili, Liu Xijun, Zhuo Longchao, Song Jun, Sun Jiaqiang, Luo Jun, Xin Huolin L
Department of Physics and Astronomy, University of California, Irvine, Irvine, CA, 92697, USA.
Institute for New Energy Materials & Low-Carbon Technologies and Tianjin Key Lab of Photoelectric Materials & Devices, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China.
Angew Chem Int Ed Engl. 2021 Jan 4;60(1):345-350. doi: 10.1002/anie.202010159. Epub 2020 Oct 27.
The electrochemical reduction of N to NH is emerging as a promising alternative for sustainable and distributed production of NH . However, the development has been impeded by difficulties in N adsorption, protonation of NN, and inhibition of competing hydrogen evolution. To address the issues, we design a catalyst with diatomic Pd-Cu sites on N-doped carbon by modulation of single-atom Pd sites with Cu. The introduction of Cu not only shifts the partial density of states of Pd toward the Fermi level but also promotes the d-2π coupling between Pd and adsorbed N , leading to enhanced chemisorption and activated protonation of N , and suppressed hydrogen evolution. As a result, the catalyst achieves a high Faradaic efficiency of 24.8±0.8 % and a desirable NH yield rate of 69.2±2.5 μg h mg , far outperforming the individual single-atom Pd catalyst. This work paves a pathway of engineering single-atom-based electrocatalysts for enhanced ammonia electrosynthesis.
将氮气电化学还原为氨正成为可持续和分布式生产氨的一种有前景的替代方法。然而，该技术的发展受到氮气吸附困难、NN的质子化以及竞争性析氢抑制等问题的阻碍。为了解决这些问题，我们通过用铜调制单原子钯位点，设计了一种在氮掺杂碳上具有双原子钯 - 铜位点的催化剂。铜的引入不仅使钯的部分态密度向费米能级移动，还促进了钯与吸附氮之间的d - 2π耦合，导致氮的化学吸附增强和质子化活化，同时抑制了析氢。结果，该催化剂实现了24.8±0.8 %的高法拉第效率和69.2±2.5 μg h mg 的理想氨产率，远远超过单个单原子钯催化剂。这项工作为设计用于增强氨电合成的单原子基电催化剂开辟了一条途径。
