Sun Qiangqiang, Dong Yujuan, Wang Zenglin, Yin Shiwei, Zhao Chuan
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, China.
Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shangluo University, Shangluo, 726000, China.
Small. 2018 Apr;14(14):e1704137. doi: 10.1002/smll.201704137. Epub 2018 Feb 27.
Developing highly active electrocatalysts with low cost and high efficiency for hydrogen evolution reactions (HERs) is of great significance for industrial water electrolysis. Herein, a 3D hierarchically structured nanotubular copper-doped nickel catalyst on nickel foam (NF) for HER is reported, denoted as Ni(Cu), via facile electrodeposition and selective electrochemical dealloying. The as-prepared Ni(Cu)/NF electrode holds superlarge electrochemical active surface area and exhibits Pt-like electrocatalytic activity for HER, displaying an overpotential of merely 27 mV to achieve a current density of 10 mA cm and an extremely small Tafel slope of 33.3 mV dec in 1 m KOH solution. The Ni(Cu)/NF electrode also shows excellent durability and robustness in both continuous and intermittent bulk water electrolysis. Density functional theory calculations suggest that Cu substitution and the formation of NiO on the surface leads to more optimal free energy for hydrogen adsorption. The lattice distortion of Ni caused by Cu substitution, the increased interfacial activity induced by surface oxidation of nanoporous Ni, and numerous active sites at Ni atom offered by the 3D hierarchical porous structure, all contribute to the dramatically enhanced catalytic performance. Benefiting from the facile, scalable preparation method, this highly efficient and robust Ni(Cu)/NF electrocatalyst holds great promise for industrial water-alkali electrolysis.
开发低成本、高效率的析氢反应(HER)高活性电催化剂对工业水电解具有重要意义。在此,通过简便的电沉积和选择性电化学脱合金法,报道了一种用于HER的三维分层结构的泡沫镍(NF)负载的纳米管状铜掺杂镍催化剂,记为Ni(Cu)。所制备的Ni(Cu)/NF电极具有超大的电化学活性表面积,并对HER表现出类似铂的电催化活性,在1 M KOH溶液中,实现10 mA cm的电流密度时过电位仅为27 mV,塔菲尔斜率极小,为33.3 mV dec。Ni(Cu)/NF电极在连续和间歇的大量水电解中也表现出优异的耐久性和稳定性。密度泛函理论计算表明,Cu的取代和表面NiO的形成导致氢吸附的自由能更优。Cu取代引起的Ni晶格畸变、纳米多孔Ni表面氧化诱导的界面活性增加以及三维分层多孔结构提供的大量Ni原子活性位点,都有助于显著提高催化性能。受益于简便、可扩展的制备方法,这种高效且稳定的Ni(Cu)/NF电催化剂在工业水碱电解中具有巨大潜力。