Room temperature preparation of NiFe-phytic acid composite and its electrocatalytic performance for overall water splitting
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摘要: 制备高稳定性、高活性双功能催化剂用于全解水制氢是氢能源大规模商业化应用的重要环节之一。本文以植酸(PA)、六水合氯化铁(FeCl3·6H2O)和六水合氯化镍(NiCl2·6H2O)为原料,采用两步室温浸渍法在泡沫镍(NF)上制备了片状无定形植酸-镍铁双金属复合材料(NiFe-PA)。采用线性扫描伏安法(LSV)考察了NiFe-PA修饰NF电极(NiFe-PA/NF)在碱性条件(1.0 mol/L KOH)的电解水催化性能。实验结果表明:由于NiFe双金属之间的协同效应,NiFe-PA/NF作为双功能催化剂显示出优越的析氧和析氢性能。NiFe-PA/NF电极在50 mA·cm−2电流密度下析氧反应的过电位仅需220 mV;在10 mA·cm−2电流密度下的析氢反应的过电位为135 mV。将NiFe-PA/NF组装成双电极系统用于全解水,达到10 mA·cm−2电流密度的电池电压仅需1.61 V,低于贵金属催化剂体系RuO2/NF||Pt-C/NF(1.64 V),同时,可满足2 V太阳能电池板在太阳光照条件下的驱动产氢。另外,基于PA金属配合物的高稳定性和抗腐蚀性能,NiFe-PA/NF在100 mA·cm−2电流密度下的析氧反应和析氢反应催化稳定性可至少分别维持175 h和75 h,表明NiFe-PA/NF在高电流密度下具有高催化稳定性。Abstract: The preparation of bifunctional catalysts with high stability and high activity for hydrogen production from water is one of the important step in the large-scale commercial application of hydrogen energy. Herein, the flake amorphous phytic acid-nickel iron bimetallic composite (NiFe-PA) has been prepared on foamed nickel (NF) by two-step room temperature impregnation using phytic acid (PA), ferric chloride hexahydrate (FeCl3·6H2O) and nickel chloride hexahydrate (NiCl2·6H2O) as the starting materials. The electrocatalytic performance of NiFe-PA modified NF electrode (NiFe-PA/NF) for water electrolysis in alkaline condition (1.0 mol/L KOH) was investigated by linear sweep voltammetry (LSV). The results show that NiFe-PA/NF, as a bifunctional catalyst, has excellent oxygen and hydrogen evolution properties due to the synergistic effect between Ni and Fe. The overpotentials are only 220 mV at 50 mA·cm−2 for oxygen evolution reaction (OER) and 135 mV at 10 mA·cm−2 hydrogen evolution reaction (HER). The NiFe-PA/NFs were then assembled into a two-electrode system for overall water splitting, and the cell voltage required to reach the current density of 10 mA·cm−2 was only 1.61 V, which is lower than the precious metal catalyst system of RuO2/NF||Pt-C/NF (1.64 V). It can also satisfy the hydrogen production driven by solar panels (2 V) under solar illumination conditions. Furthermore, owing to the high stability and corrosion resistance of the PA-metal complex, the catalytic stability of NiFe-PA/NF can be maintained at least for 175 h and 75 h, respectively, for the OER and HER at 100 mA·cm−2, indicating the high catalytic stability of NiFe-PA/NF at high current densities.
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Key words:
- bimetallic NiFe /
- phytic acid /
- overall water splitting /
- high stability /
- solar energy driven
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图 5 NiFe-PA/NF、Ni-PA/NF、Fe-PA/NF、PA/NF、RuO2/NF和NF在1.0 mol/L KOH电解液中析氧反应(OER)的LSV曲线(a)及相应的Tafel斜率曲线(b);NiFe-PA/NF在CV循环2000圈前后的LSV对比曲线(c)及在电流密度 (j) 为100 mA·cm−2下的电位-时间(P-t)曲线(d)
Figure 5. LSV curves of NiFe-PA/NF, PA/NF, Ni-PA/NF, Fe-PA/NF, RuO2/NF and NF in 1.0 mol/L KOH for oxygen evolution reaction (OER) (a), and the corresponding Tafel slope curves (b); Comparison of LSV curves of NiFe-PA/NF before and after 2000 cycles of CV (c) and the potential-time (P-t) curve at current density (j) of 100 mA·cm−2 (d)
图 6 NiFe-PA/NF、Ni-PA/NF、Fe-PA/NF、PA/NF、Pt-C/NF和NF在1.0 mol/L KOH电解液中的析氢(HER) LSV曲线(a)及相对应的Tafel斜率曲线(b);NiFe-PA/NF在CV循环2000圈前后的LSV曲线(c)和在−100 mA·cm−2下的电压-时间(P-t)曲线(d)
Figure 6. LSV curves of NiFe-PA/NF, PA/NF, Ni-PA/NF, Fe-PA/NF, Pt-C/NF and NF in 1.0 mol/L KOH for hydrogen evolution reaction (HER) (a), and the corresponding Tafel curves (b); LSVs of NiFe-PA/NF before and after 2000 cycles of CV (c), and its potential-time (P-t) curve at −100 mA·cm−2 (d)
图 8 NiFe-PA/NF、Ni-PA/NF、Fe-PA/NF、PA/NF和NF在0.55 V (a)、−1.05 V (b) (vs. Hg/HgO)下的电化学阻抗谱图(EIS);NiFe-PA/NF在不同扫速下的循环伏安(CV)曲线(c);NiFe-PA/NF、Ni-PA/NF、Fe-PA/NF、PA/NF和NF在0.98 V(vs. RHE)电位下阳极和阴极电流密度差值(Δj)与扫速的关系曲线(d)
Figure 8. Electrochemical impedence spectra (EIS) of NiFe-PA/NF, Ni-PA/NF, Fe-PA/NF, PA/NF and NF at 0.55 V (a) and −1.05 V (b) (vs. Hg/HgO), respectively; Cyclic voltammetric (CV) curves of NiFe-PA/NF at different scanning rates (c); Relationships of current density difference (Δj) of anode and cathode and scan rates at 0.98 V (vs. RHE) of NiFe-PA/NF, Ni-PA/NF, Fe-PA/NF, PA/NF and NF (d)
图 9 (a)不同电极的全解水LSV曲线;(b) NiFe-PA/NF||NiFe-PA/NF电池在10 mA·cm−2电流密度下进行的P-t测试图(插图为NiFe-PA/NF||NiFe-PA/NF两电极系统连接太阳能电池板(电压输出:2V)的电解水装置图)
Figure 9. (a) LSV curves of the overall water electrolysis by different electrodes; (b) P-t curve of NiFe-PA/NF||NiFe-PA/NF at the current density of 10 mA·cm−2 ( Inset: overall water electrolysis with NiFe-PA/NF||NiFe-PA/NF driven by solar cell (Voltage output: 2 V))
表 1 NiFe-PA与文献中铁基双功能催化剂性能比较
Table 1. Comparisons of catalytic performance between NiFe-PA and the reported Fe-based bifunctional catalysts
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