Ju HyungKuk, Seo Dong Han, Chung Sunki, Mao Xin, An Byeong-Seon, Musameh Mustafa, Gengenbach Thomas R, Shon Hokyong, Du Aijun, Bendavid Avi, Ostrikov Kostya Ken, Yoon Hyung Chul, Lee Jaeyoung, Giddey Sarbjit
Hydrogen Research Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon 34129, Republic of Korea.
CSIRO Energy, Private Bag 10, Clayton South, Victoria, 3169, Australia.
Nanoscale. 2022 Jan 27;14(4):1395-1408. doi: 10.1039/d1nr06411h.
The electrochemical synthesis of ammonia at ambient temperature and pressure has the potential to replace the conventional process for the production of ammonia. However, the low ammonia yield and poor long-term stability of catalysts for the synthesis of ammonia hinders the application of this technology. Herein, we endeavored to tackle this challenge by synthesizing 3-D vertical graphene (VG) on Ni foam a one-step, low-temperature plasma process, which offered high conductivity and large surface area. Subsequently, the vertical graphene on Ni foam was loaded with nanolayers of ruthenium oxide (RuO, ∼2 nm) and cerium oxide (CeO, <20 nm) nanoparticles magnetron sputtering. The incorporation of nanoparticle layers (RuO and CeO/RuO) on VG significantly increased the NH yield in KOH electrolyte. Finally, the performance and long-term stability of this composite material were successfully demonstrated by the addition of CeO/RuO nanolayers on the VG electrocatalyst. The catalyst achieved an excellent performance with a high ammonia synthesis yield of 50.56 μg mg h (1.11 × 10 mol cm s) during the performance evaluation period of 36 h. This observation was also verified by density functional theory calculation, where CeO exhibited the best catalytic performance compared to RuO and pristine graphene.
在常温常压下电化学合成氨有潜力取代传统的氨生产工艺。然而,用于合成氨的催化剂氨产率低且长期稳定性差,这阻碍了该技术的应用。在此,我们通过一步低温等离子体工艺在泡沫镍上合成三维垂直石墨烯(VG)来应对这一挑战,该工艺具有高导电性和大表面积。随后,通过磁控溅射在泡沫镍上的垂直石墨烯上负载氧化钌(RuO,约2纳米)和氧化铈(CeO,<20纳米)纳米颗粒的纳米层。在VG上引入纳米颗粒层(RuO和CeO/RuO)显著提高了KOH电解液中的NH产率。最后,通过在VG电催化剂上添加CeO/RuO纳米层成功证明了这种复合材料的性能和长期稳定性。在36小时的性能评估期内,该催化剂实现了优异的性能,氨合成产率高达50.56μg mg h(1.11×10 mol cm s)。密度泛函理论计算也验证了这一观察结果,其中与RuO和原始石墨烯相比,CeO表现出最佳的催化性能。