多孔碳负载钌单原子和钌纳米团簇催化剂用于高效析氢反应

Porous carbon supported ruthenium single atom and ruthenium nanoclusters catalysts for efficient hydrogen evolution reaction

  • 摘要: 高效析氢反应(HER)电催化剂的制备对氢能的大规模推广具有重大的意义。本文以羧甲基纤维素钠(CMC-Na)和RuCl3为原料,利用Ru离子与CMC-Na在溶液中配位制备了Ru-CMC-Na水凝胶,随后通过冷冻干燥、高温退火和酸洗制备了多孔碳负载Ru单原子和Ru纳米团簇的催化剂RuSA+NC/C-2。催化剂RuSA+NC/C-2在酸性和碱性电解质中都具有优异的HER活性和稳定性,达到10 mA·cm−2电流密度,所需过电位分别20 mV和23 mV,经过12 h的恒电位测试其活性未见明显衰减。催化剂RuSA+NC/C-2中Ru的含量为5.52wt%,在1 mol/L KOH电解质中,过电位为0.05 V时,催化剂的质量活性是商业Pt/C的5.8倍。通过对催化剂RuSA+NC/C-2的物理表征测试发现,催化剂RuSA+NC/C-2的多孔结构和大比表面积,可以暴露更多的活性位点。Ru单原子与Ru纳米团簇结构提高了Ru原子的利用率。通过XPS分析,Ru与碳载体间存在强相互作用,形成了缺电子态的Ru,从而提高了催化剂的HER活性。

     

    Abstract: The preparation of electrocatalyst for high efficiency hydrogen evolution reaction (HER) is of great significance to the large-scale promotion of hydrogen energy. In this paper, using sodium carboxymethyl cellulose (CMC-NA) and RuCl3 as raw materials, Ru-CMC-Na hydrogel was prepared by the coordination of Ru ions with CMC-Na in solution. Then, porous carbon supported Ru single atom and Ru nanocluster catalyst RuSA+NC/C-2 was prepared by freeze-drying, high temperature annealing and pickling. The catalyst RuSA+NC/C-2 shows excellent HER activity and stability in both acidic and alkaline electrolytes, reaching 10 mA·cm−2 current density at 20 mV and 23 mV, respectively. After 12 h chronoamperometry test, the activity of RuSA+NC/C-2 shows no obvious attenuation. The mass activity of RuSA+NC/C-2 is 5.8 times that of commercial Pt/C when the overpotential is 0.05 V in 1 mol/L KOH electrolyte. The physical characterization of RuSA+NC/C-2 catalyst shows that the porous structure and large specific surface area of RuSA+NC/C-2 catalyst can expose more active sites. Ru single atom and Ru nanocluster structure improve the utilization rate of Ru atom. XPS analysis shows that there is a strong interaction between Ru and carbon support, resulting in the formation of electron-deficient Ru, thus improving HER activity of the catalyst.

     

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