Synthesis and electrocatalytic oxygen evolution performances of high conductivity silver nanowire@polypyrrole@CoNi alloy aerogels
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摘要: 针对传统贵金属析氧反应(OER)电催化剂的电导率较低、催化活性较差、成本高等问题，开发高效耐久、低成本且具有高暴露活性表面和优良导电性的电催化剂已迫在眉睫。通过冷冻干燥法合成银纳米线@聚吡咯(AgNWs@PPy)气凝胶，然后使用溶剂热法在AgNWs@PPy气凝胶骨架表面生长纳米CoNi合金，获得了OER电催化性能良好的AgNWs@PPy@CoNi气凝胶。结果表明，随着Co2+、Ni2+浓度的增加，AgNWs@PPy@CoNi气凝胶的催化性能先增强后减弱，当Co2+、Ni2+浓度为0.0175 mol/L制备的AgNWs@PPy@CoNi气凝胶在电流密度10 mA·cm−2时，过电位为346 mV，Tafel斜率为86.25 mV·dec−1，在恒定电压下经过10 h的稳定性测试，电流保持率达93.9%，具有良好的稳定性。三维独立型AgNWs@PPy气凝胶提供优良的导电性，CoNi合金提供丰富的活性位点，二者的共同作用表现出优异的OER催化性能，将有望替代贵金属催化剂而成为新型的OER催化材料。
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关键词:
- 溶剂热 /
- CoNi合金 /
- AgNWs@PPy气凝胶 /
- 电催化 /
- 析氧反应
Abstract: Given the low conductivity, poor catalytic activity, and high cost of traditional noble metal-oxygen evolution reaction (OER) electrocatalysts, it is urgent to develop electrocatalysts with high efficiency, durability, low cost, high exposed active surface, and excellent electrical conductivity. The Silver nanowire@Polypyrrole (AgNWs@PPy) aerogels were synthesized by freeze-drying method, and then nano-CoNi alloy was grown on the surface of AgNWs@PPy aerogels framework by solvothermal method, and AgNWs@PPy@CoNi aerogels with good OER electrocatalytic performance was obtained. The results show that the catalytic performance of AgNWs@PPy@CoNi aerogels first increase and then weaken with the increase of Co2+ and Ni2+ concentrations. When the Co2+ and Ni2+ concentrations are 0.0175 mol/L, the AgNWs@PPy@CoNi aerogels exhibite high current density. At 10 mA·cm−2, the overpotential is 346 mV, and the Tafel slope is 86.25 mV·dec−1. After a 10-hour stability test under a constant voltage, the current retention rate reaches 93.9%, which has good stability. The three-dimensional independent AgNWs@PPy aerogels provide excellent electrical conductivity, and the CoNi alloy provides abundant active sites. The combined effect of them shows excellent OER catalytic performance, which is expected to replace precious metal catalysts and become a new type of OER catalytic material.-
Key words:
- solvothermal method /
- CoNi alloy /
- AgNWs@PPy aerogels /
- electrocatalysis /
- OER
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图 1 AgNWs@PPy气凝胶和AgNWs@PPy@CoNi气凝胶制备工艺示意图
Figure 1. Schematic illustration for the fabrication process of Ag@PPy aerogels and Ag@PPy@CoNi aerogels
PPy—Polypyrrole; Py—Pyrrole; AgNWs—Silver nanowire
图 2 AgNWs@PPy@CoNi气凝胶的照片：(a)挤压时；(b)压力去除后
Figure 2. Naked eye photos of AgNWs@PPy@CoNi aerogels: (a) compressing; (b) removing compression
图 3 高长径比AgNWs (a)和AgNWs@PPy气凝胶(b)的SEM图像；(c) AgNWs@PPy气凝胶的TEM图像
Figure 3. SEM images of high aspect ratio AgNWs (a) and AgNWs@PPy aerogels (b); (c) TEM image of AgNWs@PPy aerogels
图 4 Py浓度对AgNWs@PPy气凝胶形貌的影响
Figure 4. Influence of Py concentration on the morphology of AgNWs@PPy aerogels
图 5 不同浓度AgNWs@PPy@CoNi气凝胶的SEM图像
Figure 5. SEM images of AgNWs@PPy@CoNi aerogels with different concentrations
图 6 AgNWs@PPy@CoNi气凝胶的TEM图像(插图是SAED模式) (a)、HRTEM图像(b)、元素分布图像((c)~(f))和EDS能谱(g)
Figure 6. TEM image (inset is SAED image pattern) (a), HRTEM image (b), elemental mapping images ((c)-(f)) and EDS spectrum (g) of AgNWs@PPy@CoNi aerogels
图 7 AgNWs@PPy@CoNi气凝胶的XRD图谱(a)和FTIR图谱(b)
Figure 7. XRD pattern (a) and FTIR spectrum (b) of AgNWs@PPy@CoNi aerogels
图 8 AgNWs@PPy@CoNi气凝胶XPS图谱(a)和Ag3d (b)、Co2p (c)、Ni2p (d)的高分辨率XPS图谱
Figure 8. XPS survey spectrum (a) and high-resolution XPS spectra of Ag3d (b), Co2p (c), Ni2p (d) for Ag@PPy@CoNi aerogels
图 9 AgNWs@PPy气凝胶、CoNi合金和AgNWs@PPy@CoNi气凝胶在0.1 mol/L KOH溶液中LSV图(a)和在10 mA·cm−2时OER的过电位(b)
Figure 9. LSV diagram (a) and OER overpotential (b) at 10 mA·cm−2 of AgNWs@PPy aerogels, CoNi alloys and AgNWs@PPy@CoNi aerogels in 0.1 mol/L KOH solution
图 10 由LSV曲线导出的AgNWs@PPy气凝胶、CoNi合金以及AgNWs@PPy@CoNi气凝胶的Tafel斜率
Figure 10. Tafel slope of AgNWs@PPy aerogels, CoNi alloy and AgNWs@PPy@CoNi aerogels derived from LSV curve
图 11 AgNWs@PPy气凝胶、CoNi合金及AgNWs@PPy@CoNi气凝胶在0.1 mol/L KOH溶液中EIS图
Figure 11. EIS diagram of AgNWs@PPy aerogels, CoNi allo and AgNWs@PPy@CoNi aerogels in 0.1 mol/L KOH solution
图 12 AgNWs@PPy@CoNi气凝胶与其他Ag基电催化剂在10 mA·cm−2下的过电位和塔菲尔斜率的对比图
Figure 12. Comparison of overpotential and Tafel slope between AgNWs@PPy@CoNi aerogels and other Ag-based electrocatalysts at 10 mA·cm−2
BSCF-Ag—Silver doped Ba0.5Sr0.5Co0.8Fe0.2O3-δ; Ag-Co/FTO—Ag-doped Co3O4 nanowire arrays supported on FTO fluorine-doped tin oxide; Ag-Ci—Catalyst containing silver and carbon
图 13 浓度为0.0175 mol/L的AgNWs@PPy@CoNi气凝胶在500圈CV前后的LSV曲线；插图为浓度0.0175 mol/L的样品在过电位为346 mV时进行10 h的稳定性实验
Figure 13. LSV curve of the 0.0175 mol/L AgNWs@PPy@CoNi aerogels before and after 500 cycles of CV; Inset shows that a sample with a concentration of 0.0175 mol/L was subjected to a stability experiment for 10 h at an overpotential of 346 mV
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