基于配合物前驱体的CuO原位制备与电催化产氧活性研究

doi:10.7517/j.issn.1674-0475.2015.05.403

摘要/Abstract

摘要：

合成得到了含有N,N,N',N'-四羟乙基乙二胺(THEED)配体的Cu(Ⅱ)配合物[Cu(THEED)(H₂O)]SO₄,通过质谱、元素分析以及X-射线单晶衍射测定了它的组成和晶体结构,并用之作为电催化产氧催化剂的前驱体。在电解含有配合物的碱性NaOAc/NaOH溶液时可检测到氧气产生,并发现有黑色薄膜附着于阳极表面。利用扫描电子显微镜(SEM)、能量色散X射线(EDX)、X射线衍射(XRD)和X射线光电子能谱(XPS)确定该薄膜的主要成分是2 μm大小的无定形CuO颗粒。通过实验证明,CuO为真正的电催化水氧化催化剂,它具有较高活性和稳定性。在无Cu(Ⅱ)、0.10 mol/L NaOAc/NaOH溶液(pH=12.4)中,固定催化电压为1.35 V(相对于标准氢电极电压),催化电流密度可维持1.5 mA/cm²近6 h不变;7.5 h产生氧气97 μmol,法拉第效率95%。

关键词: N, N, N', N'-四羟乙基乙二胺, Cu(Ⅱ)配合物, CuO, 电催化, 水氧化

Abstract:

Cu(Ⅱ) complex containing N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and water ligands, [Cu(THEED)(H₂O)]SO₄, was synthesized and structurally characterized by electrospray ionization mass spectrometry, elemental analysis and X-ray crystal analysis. Electrocatalytic investigation in basic NaOAc/NaOH solution with the complex found that a black film on the surface of anodic electrode was produced. Oxygen was formed and detected by GC analysis. The film was characterized by scanning electron microscopy, energy-dispersive X-ray analysis, X-ray powder diffraction and X-ray photoelectron spectroscopy. The experimental results revealed that the major component of the black solid is amorphous CuO. Further studies proved that [Cu(THEED)(H₂O)]SO₄ is a precursor, while CuO is the real water oxidation catalyst with high activity and stability. The catalytic performance of the film is demonstrated by longer term electrolysis at pH 12.4 and 1.35 V vs normal hydrogen electrode.The current density was retaining at 1.5 mA/cm² at least 6 hours; about 97 μmol oxygen was produced after a 7.5 h electrolysis and 95% Faradaic efficiency was achieved.

Key words: N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, Cu(Ⅱ) complex, CuO, eletrocatalysis, water oxidation

蔡溶, 傅文甫. 基于配合物前驱体的CuO原位制备与电催化产氧活性研究[J]. 影像科学与光化学, 2015, 33(5): 403-410.

CAI Rong, FU Wenfu. Highly Active CuO Water Oxidation Catalyst Electrodeposited from a Copper(Ⅱ) Complex[J]. Imaging Science and Photochemistry, 2015, 33(5): 403-410.

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