Ambient Ammonia Electrosynthesis from Nitrogen and Water by Incorporating Palladium in Bimetallic Gold–Silver Nanocages
Ambient Ammonia Electrosynthesis from Nitrogen and Water by Incorporating Palladium in Bimetallic Gold–Silver Nanocages
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DOI：
10.1149/1945-7111/ab6ee9
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发表时间：
2020-02
影响因子：
3.9
通讯作者：
M. Nazemi;Luke Soule;Meilin Liu;M. El-Sayed
中科院分区：
文献类型：
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作者：
M. Nazemi;Luke Soule;Meilin Liu;M. El-Sayed
当电力由可再生能源产生时，使用氮气和水的氨电合成以清洁、可持续和分散的方式提供了热化学过程（Haber-Bosch）的潜在替代方案。为了使这项技术能够广泛商业化，必须开发一种高选择性和高活性的将氮气（N2）转化为氨（NH3）的电催化剂。在这里，我们报告了我们在研究中发现的将钯（Pd）掺入到Au-Ag纳米笼中对环境条件下氮还原反应（NRR）的电催化活性的作用。所得三金属纳米颗粒的局部表面等离子体共振（LSPR）峰位置随Pd浓度而调谐，使用Au-Ag-Pd-850纳米颗粒在− 0.3 V vs RHE下实现最高的电催化NRR活性（NH3产率= 48.94%）。该活动对应于28.9%的生产能源效率，电能输入为19.1 MWh /吨NH3。增强的NRR活性主要归因于形成具有显著高的NRR活性表面积的高度多孔的Pd层。此外，操作表面增强拉曼光谱（Sers）被用来探测三金属纳米结构上的NRR的机制，并确定在电极-电解质界面的中间物种。在0.5 M LiClO（aq.）溶液由于Ag的置换率为0.65（高于0.5（相对于RHE））但低于V（相对于RHE），因此在电流置换过程中，只有在加入Pd盐（K2 PdCl 4（aq.））在Au-Ag纳米结构模板中。三金属纳米结构的LSPR峰位置的红移表明用Pd取代Ag或Pd在Au上生长。我们还报告了使用我们合成的纳米催化剂在N2电解系统中氨的能量输入（MWh吨-1 NH3）和生产能量效率（%），并将我们的结果与
Electrosynthesis of ammonia using nitrogen and water provides a potential alternative to the thermochemical process (Haber- Bosch) in a clean, sustainable, and decentralized way when electricity is generated from renewable sources. To enable the widespread commercialization of this technology, an electrocatalyst to convert nitrogen (N 2 ) to ammonia (NH 3 ) with high selectivity and activity must be developed. Here, we report our fi ndings in the investigation into the role of incorporating palladium (Pd) in bimetallic Au-Ag nanocages on the electrocatalytic activity of the nitrogen reduction reaction (NRR) under ambient conditions. The localized surface plasmon resonance (LSPR) peak position of the resulting trimetallic nanoparticles is tuned with Pd concentration, achieving the highest electrocatalytic NRR activity (NH 3 yield = 48.94%) using Au-Ag-Pd-850 nanoparticles at − 0.3 V vs RHE. This activity corresponds to the production energy ef fi ciency of 28.9% with an electrical energy input of 19.1 MWh / ton NH3 . The enhanced NRR activity is attributed mainly to the formation of a highly porous Pd layer with remarkably high surface area active for NRR. In addition, operando surface-enhanced Raman spectroscopy (SERS) is used to probe the mechanism of NRR on the trimetallic nanostructures and to identify the intermediate species at the electrode-electrolyte interface. bimetallic Au-Ag nanostructures on the electrocatalytic NRR activity in 0.5 M LiClO (aq.) solution. Since the of ∼ 0.65 vs higher 0.5 vs RHE) but lower than V vs RHE), Ag can only be replaced with Pd in the galvanic replacement process after the addition of Pd salt (K 2 PdCl 4 (aq.)) in the bimetallic Au-Ag nanostructures template. The red shifting of the LSPR peak position of the trimetallic nanostructures indicates either the replacement of Ag with Pd or the growth of Pd on Au. We also report energy input (MWh ton − 1 NH3 ) and production energy ef fi ciency (%) of ammonia in the N 2 electrolysis system using our synthesized nanocatalysts, and we compare our results with the