Bimetallic oxynitride-Co single atom composite electrocatalyst synergistically improve oxygen reduction reaction in wide pH range
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摘要: 本论文基于传统聚合物基炭材料合成原理,通过选择合适结构的前驱体分子,在聚合过程中分子水平锚定Co原子,同时引入TiO2纳米颗粒,再经高温焙烧后制得一种双金属氮氧化物(ComTinOxNy)-Co单原子(Co-NC)复合催化剂。该催化剂在酸性(Eonset = 0.755 V vs. RHE,0.5 mol/L H2SO4; 0.760 V vs. RHE,0.1 mol/L HClO4)、中性(Eonset = 0.787 V vs. RHE,0.1 mol/L PBS)、碱性(Eonset = 0.880 V vs. RHE,0.1 mol/L KOH)电解液中的氧气还原(ORR)性能(pH = 0−13)均优于纯氮杂碳纳米管、氮杂碳纳米管负载的金属氮氧化物和Co单原子催化剂,表明,ComTinOxNy与Co单原子的协同效应使得复合催化剂具有更好的ORR活性,同时复合催化剂的稳定性和选择性显著优于商品Pt/C催化剂。这为开发高性能低成本氧气还原电催化剂提供了新的思路。Abstract: The lack of high performance and low cost oxygen reduction electrocatalysts, especially operating in the wide pH range, is one of the key obstacles restricting the large-scale applications of new energy conversion technologies such as fuel cells and metal-air batteries. In this work, based on the synthesis mechanism of conventional polymer-derived carbon materials, a bimetallic oxy-nitride (ComTinOxNy)-Co single atom (Co-NC) composite catalyst was prepared by an associated hydrothermal polymerization-pyrolysis method through selecting suitable precursor molecules and simultaneously introducing TiO2 nanoparticle in the process of polymerization. The bimetallic cobalt-titanium oxy-nitride Co-NC composite catalyst exhibits better ORR activity in a wide pH range (0−13) than the conresponding pure N-doped carbon nanotubes, titanium oxy-nitride/N-CNTs and Co-NC catalysts, providing a new idea for the development of ORR electrocatalysts with high performance and low cost.
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Key words:
- bimetallic oxy-nitride /
- co-single atom /
- oxygen reduction reaction /
- synergistic effect
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图 6 (a)LSV曲线,(b)Koutecký-Levich图,((c),(d))Co/Ti-NC-300的旋转环盘电极测试,(e)甲醇交叉效应测试和(f)0.1 mol/L KOH中Co/Ti-NC-300和Pt/c催化剂的稳定性测试
Figure 6 (a) Linear sweep voltametry (LSV) curves, (b) Koutecký-Levich plots, ((c), (d)) Rotating ring-disk electrode test of Co/Ti-NC-300, (e) methanol crossing effect tests and (f) stability measurements of Co/Ti-NC-300 and Pt/C catalysts measured in 0.1 mol/L KOH
图 7 Co/Ti-300在0.1 mol/L KOH中测试20 h后的XPS光谱:(a)Ti 2p,(b)N 1s,(c)Co 2p高分辨率光谱;(d)Co/Ti-300分别在0.5 mol/L H2SO4、0.1 mol/L HClO4、0.1 mol/L PBS和0.1 mol/L KOH中测试的LSV曲线
Figure 7 XPS spectra of Co/Ti-300 after 20 h measurement in 0.1 mol/L KOH: (a) Ti 2p, (b) N 1s, (c) Co 2p high-resolution spectra; (d) LSV curves of Co/Ti-NC-300 measured in 0.5 mol/L H2SO4, 0.1 mol/L HClO4, 0.1 mol/L PBS and 0.1 mol/L KOH, respectively
表 1 不同催化剂的电化学性能参数
Table 1 Electrochemical parameters of different catalysts
Sample E1/2 /(mV vs. RHE) Eonset /(mV vs. RHE) j0 /(mA·cm−2) jk /(mA·cm−2)@0.5 V vs. RHE b /(mV·dec−1) Co/Ti-NC-300 800 880 35.2 × 10−9 15.20 54 Ti-NC 707 822 119 × 10−9 8.72 68 Co -NC 808 885 6.79 × 10−9 12.01 48 Pt/C 837 958 2383 × 10−9 71.61 59 -
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