4 d Metal-doped liquid Ga for efficient ammonia electrosynthesis at wide N2 concentrations

doi:10.1016/S1872-2067(24)60144-0

Abstract

Abstract:

Electrocatalytic nitrogen reduction reaction under ambient conditions is a promising pathway for ammonia synthesis. Currently nitrogen reduction reactions are carried out in N₂-saturated environments and use high-purity nitrogen as feedstock, which is costly. Here, we prepared carbon-coated ultra-low 4d metal Ru-doped liquid metal Ga (Ru_0.06/LM@C) for NRR over a wide range of N₂ concentrations. Comprehensive analyses show that the introduction of the ultra-low 4d element Ru can effectively adjust the electronic structure through orbital interactions, thus enhancing the adsorption of nitrogen-containing intermediates. The liquid catalyst utilized its mobility to provide a higher density of active sites. In addition, the material Ru_0.06/Ga@C itself has the ability to promote product desorption. The three act synergistically to optimize the N₂ mass transfer path, thereby increasing the *NNH coverage and further improving the ammonia yield over a wide range of N₂ concentrations. The maximum NH₃ yield of the catalyst can reach 126.0 μg h^-1 mg_cat^-1 (at -0.3 V vs. RHE) with high purity N₂ as feed gas, and the Faraday efficiency is 60.4% at -0.1 V vs. RHE. Over a wide range of N₂ concentrations, the NH₃ yield of the catalyst was greater than 100 μg h^-1 mg_cat^-1 with a Faraday efficiency higher than 47%. The catalytic performance is much higher than that of solid Ga@C and reported p-block metal-based catalysts.

Key words: Liquid catalyst, Electrocatalysis, Nitrogen reduction reaction, Ammonia synthesis, Electrocatalyst

Yingying Wei, Yuyao Sun, Yaodong Yu, Yue Shi, Zhe Wu, Lei Wang, Jianping Lai. 4 d Metal-doped liquid Ga for efficient ammonia electrosynthesis at wide N₂ concentrations[J]. Chinese Journal of Catalysis, 2024, 67: 194-203.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60144-0

https://www.cjcatal.com/EN/Y2024/V67/I12/194

Figures/Tables 5

Fig. 1. Morphology and composition characterizations of Ru0.06/LM@C catalyst. (a) SEM image. (b) TEM image. (c) The corresponding EDS elemental mappings. HRTEM image (d) and enlarged images (e). (f) XRD patterns. XPS spectra of the Ru0.06/LM@C catalyst: (g) Ga 2p; (h) Ru 3p1/2; (i) C 1s.

Fig. 2. Electrochemical nitrogen reduction performance of Ru0.06/LM@C catalysts. (a) LSV curves in high-purity N2 and Ar atmospheres. (b) The obtained NH3 yield and corresponding FEs at the given potential in high-purity N2 atmospheres with a constant flow rate of 30 mL min-1. (c) NH3 yield and FE at different N2 partial pressures. (d) Comparison of the NRR performance of Ru0.06/LM@C with that of other reported catalysts. The orange balls represent the performance of this work. The unit of NH3 yield in the graph is μg h-1 mgcat-1. (e) Recycling test for 12 times of Ru0.06/LM@C catalyst at -0.3 V vs. RHE.

Fig. 3. Performance of Ru0.06/LM@C catalyst on AEM electrolyzer. (a) Schematic diagram of the AEM electrolyzer. (b) LSV curves of Ru0.06/LM@C (-) || RuO2 (+) in the AEM electrolyzer. (c) Current density-dependent FE and voltage in an AEM electrolyser. Error bars represent the standard deviation of three independent measurements. (d) Chronoamperometric current curves of Ru0.06/LM@C (-) || RuO2 (+) at a cell voltage of 1.7 V (blue dots are Ammonia FE, green line is current density).

Fig. 4. DFT calculation. (a) Free energy of H2O dissociation process on Ga@C and Ru0.06/Ga@C. (b) The charge difference of N2 adsorbed on Ga@C (left) and Ru0.06/Ga@C (right). (c) The DOS patterns of Ga@C. (d) The DOS patterns of Ru0.06/Ga@C. (e) Gibbs free energy diagrams of NRR on the Ru0.06/Ga@C and Ga@C.

Fig. 5. Exploration of NRR mechanism on Ru0.06/LM@C. (a) In situ FTIR spectra of Ru0.06/LM@C catalyst in 0.1 mol L?1 KOH at different potentials. (b) The variable temperature in situ FTIR spectra. (c) N2-TPD of Ru0.06/LM@C and Ga@C. (d) Simplification of the NH3 generation mechanism on Ru0.06/LM@C.

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4 d Metal-doped liquid Ga for efficient ammonia electrosynthesis at wide N₂ concentrations

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