Cao Meng, Xue Zhe, Niu Jingjing, Qin Jiaqian, Sawangphruk Montree, Zhang Xinyu, Liu Riping
State Key Laboratory of Metastable Materials Science and Technology , Yanshan University , Qinhuangdao 066004 , P. R. China.
Research Unit of Advanced Materials for Energy Storage, Metallurgy and Materials Science Research Institute , Chulalongkorn University , Bangkok 10330 , Thailand.
ACS Appl Mater Interfaces. 2018 Oct 17;10(41):35224-35233. doi: 10.1021/acsami.8b12321. Epub 2018 Oct 2.
Hydrogen can be the potential substitute energy carrier for fuel while electrolysis water with hydrogen evolution reaction (HER) is an efficient way to produce hydrogen. Highly active and robust electrocatalysts composed by earth abundant elements are required. Herein, nickel-copper-phosphorus (Ni-Cu-P) electrocatalysts are designed and synthesized by a facile one-step electrodeposition method. A unique pine-needle-like dendrite nanotube morphology of Ni-Cu-P electrocatalyst can be synthesized when copper content changed and impressive HER activity obtained in alkaline and acidic media. Briefly, the overpotential reaches 120 mV in 1 M KOH and 150 mV in 0.5 M HSO at the current density of 10 mA cm, with the corresponding Tafel slope reaching 69 mV dec. The results are close to that of commercial Pt/C catalysts (37 mV in 1 M KOH). Furthermore, the density functional theory calculations also demonstrate that P-incorporated Ni-Cu, Cu-incorporated Ni-P, and Ni-incorporated Cu-P have the optimized hydrogen adsorption free energy (Δ G) of -0.066, -0.157, and -0.003 eV, respectively, which are more suitable than those of Ni-Cu, Ni-P, and Cu-P, respectively. The Ni-incorporated Cu-P even has a much smaller Δ G of -0.003 than that of Pt (∼-0.09 eV). We believe that our study will provide a new strategy to design non-noble metal alloy materials for practical applications in catalysis and energy fields.
氢可成为燃料的潜在替代能源载体，而通过析氢反应（HER）电解水是生产氢的有效方法。需要由储量丰富的元素组成的高活性且稳定的电催化剂。在此，通过简便的一步电沉积法设计并合成了镍 - 铜 - 磷（Ni - Cu - P）电催化剂。当铜含量变化时，可合成具有独特松针状枝晶纳米管形态的Ni - Cu - P电催化剂，并在碱性和酸性介质中获得令人印象深刻的析氢活性。简而言之，在10 mA cm²的电流密度下，在1 M KOH中过电位达到120 mV，在0.5 M H₂SO₄中达到150 mV，相应的塔菲尔斜率达到69 mV dec⁻¹。结果接近商业Pt/C催化剂（在1 M KOH中为37 mV）。此外，密度泛函理论计算还表明，掺入P的Ni - Cu、掺入Cu的Ni - P和掺入Ni的Cu - P的优化氢吸附自由能（ΔG）分别为 - 0.066、 - 0.157和 - 0.003 eV，分别比Ni - Cu、Ni - P和Cu - P更合适。掺入Ni的Cu - P甚至具有比Pt（约 - 0.09 eV）小得多的 - 0.003 eV的ΔG。我们相信我们的研究将为设计用于催化和能源领域实际应用的非贵金属合金材料提供新策略。
