ELECTRODEPOSITION OF METAL ALLOY AND MIXED-OXIDE FILMS USING A SINGLE-PRECURSOR TETRANUCLEAR COPPER-NICKEL COMPLEX
ELECTRODEPOSITION OF METAL ALLOY AND MIXED-OXIDE FILMS USING A SINGLE-PRECURSOR TETRANUCLEAR COPPER-NICKEL COMPLEX
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DOI：
10.1149/1.2049987
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发表时间：
1995-10-01
影响因子：
3.9
通讯作者：
DAVIES, G
中科院分区：
文献类型：
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作者：
DUBE, CE;WORKIE, B;DAVIES, G
异四核配合物(Mu(4)-O)L(4)Cu(4-x)Ni(X)(H2O)(X)(X)Cl6(x=1-4，L=N，N-二乙基烟酰胺)在二甲基亚砜中的铂电极上的电还原导致铜镍合金的沉积，同时铜(I)氧化物、镍(II)氧化物和镍(II)氢氧化物共沉积。合金沉积电位在复杂的化学计量比下是不变的。X-射线衍射仪测定的合金Ni含量从x=1的12%增加到x=4时的62%。显微结构粗糙、附着力良好、连续的膜层由空气氧化形成的自然钝化层由Ni(OH)(2)、NiO、Cu(OH)(2)和Cu2O组成。X射线光电子能谱证实了X射线衍射法得到的块体薄膜合金成分。数据显示了由NiO、Ni(OH)(2)、Cu2O和铜-镍合金组成的复杂的沉积结构，使络合物中的金属达到了质量平衡。铜络合物的Cu2O/Cu0比接近1，而CuNi3络合物的Cu2O/Cu0比降至零。相比之下，在铜镍合金中只有一半的Ni(II)中心以Ni-0的形式沉积，其余的由37%的NiO和15%的Ni(OH)(2)组成。所有沉积物中Ni以Ni(OH)(2)形式存在的比例不变，表明它是由Ni配位水还原而来的。质量平衡表明，Cu2O中的O和NiO来源于Mu(4)-O。合金成分、金属氧化物/金属比和薄膜颗粒大小的平滑变化表明，所有的电极过程都涉及到杂多金属络合物的离散分子。
Electroreduction of heterotetranuclear complexes (mu(4)-O)L(4)Cu(4-x)Ni(x)(H2O)(x)Cl-6 (x = 1-4, L = N,N-diethylnicotinamide) at a Pt electrode in dimethylsulfoxide leads to deposition of Cu-Ni alloys with codeposition of Cu(I) oxide, Ni(II) oxide, and Ni(II) hydroxide. The alloy deposition potential is invariant with complex stoichiometry. Alloy Ni composition, determined by x-ray diffraction (XRD), increases from 12% for x = 1 to 62% for x = 4. The microscopically rough, well-adhering, continuous films have a natural passivation layer formed by air oxidation that consists of Ni(OH)(2), NiO, Cu(OH)(2), and Cu2O. X-ray photoelectron spectroscopy confirmed the bulk film alloy compositions obtained by XRD. The data revealed complex deposit structures consisting of NiO, Ni(OH)(2), Cu2O, and Cu-Ni alloy giving a mass balance of the metals in the complexes. The Cu2O/Cu-0 ratio is close to unity for the deposit made from the Cu, complex and decreases to zero for the CuNi3 complex. In contrast only half of the Ni(II) centers are deposited as Ni-0 in the Cu-Ni alloy, the balance consisting of 37% NiO and 15% Ni(OH)(2). The constant percentage of Ni as Ni(OH)(2) in all deposits suggests that it arises from reduction of Ni coordinated water. Mass balance indicates O in Cu2O and NiO originates from the mu(4)-O. Smooth variations of alloy compositions, metal oxide/metal ratios, and film particle sizes indicate that all the electrode processes involve discrete molecules of the heteropolymetallic complex.