物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2013年
3期
491-497
,共7页
胡军%施炜%倪哲明*%刘娇%薛继龙
鬍軍%施煒%倪哲明*%劉嬌%薛繼龍
호군%시위%예철명*%류교%설계룡
密度泛函理论%铜锌镁铝四元水滑石%不同层间阴离子%超分子作用力
密度汎函理論%銅鋅鎂鋁四元水滑石%不同層間陰離子%超分子作用力
밀도범함이론%동자미려사원수활석%불동층간음리자%초분자작용력
Density functional theory%Cu-Zn-Mg-Al quaternary hydrotalcite%Different intercalated anions%Supra-molecular interaction
构建一价阴离子(X=F-, Cl-, Br-, I-, NO-3, OH-)插层铜锌镁铝四元水滑石(CuZnMgAl-X)周期性计算模型,采用密度泛函理论(DFT),选取CASTEP程序模块,对体系进行几何全优化,从结合能、结构参数、Mul iken布居、氢键布居、态密度等角度研究了不同层间阴离子的分布形态以及其对主客体间超分子作用的影响.结果表明,随着CuZnMgAl-X体系层间阴离子电负性的减弱,电子逐渐从层间阴离子向层板发生转移,主客体间静电作用力逐渐减小,氢键强度逐渐降低,禁带宽度逐渐变窄,体系电子更易向高能级发生跃迁,稳定性逐渐下降.此外, Cu的掺杂使得CuZnMgAl-X体系的价带顶向高能量处发生偏移,禁带宽度较传统水滑石体系更窄,稳定性更低,进一步解释了含铜水滑石较难合成的原因.
構建一價陰離子(X=F-, Cl-, Br-, I-, NO-3, OH-)插層銅鋅鎂鋁四元水滑石(CuZnMgAl-X)週期性計算模型,採用密度汎函理論(DFT),選取CASTEP程序模塊,對體繫進行幾何全優化,從結閤能、結構參數、Mul iken佈居、氫鍵佈居、態密度等角度研究瞭不同層間陰離子的分佈形態以及其對主客體間超分子作用的影響.結果錶明,隨著CuZnMgAl-X體繫層間陰離子電負性的減弱,電子逐漸從層間陰離子嚮層闆髮生轉移,主客體間靜電作用力逐漸減小,氫鍵彊度逐漸降低,禁帶寬度逐漸變窄,體繫電子更易嚮高能級髮生躍遷,穩定性逐漸下降.此外, Cu的摻雜使得CuZnMgAl-X體繫的價帶頂嚮高能量處髮生偏移,禁帶寬度較傳統水滑石體繫更窄,穩定性更低,進一步解釋瞭含銅水滑石較難閤成的原因.
구건일개음리자(X=F-, Cl-, Br-, I-, NO-3, OH-)삽층동자미려사원수활석(CuZnMgAl-X)주기성계산모형,채용밀도범함이론(DFT),선취CASTEP정서모괴,대체계진행궤하전우화,종결합능、결구삼수、Mul iken포거、경건포거、태밀도등각도연구료불동층간음리자적분포형태이급기대주객체간초분자작용적영향.결과표명,수착CuZnMgAl-X체계층간음리자전부성적감약,전자축점종층간음리자향층판발생전이,주객체간정전작용력축점감소,경건강도축점강저,금대관도축점변착,체계전자경역향고능급발생약천,은정성축점하강.차외, Cu적참잡사득CuZnMgAl-X체계적개대정향고능량처발생편이,금대관도교전통수활석체계경착,은정성경저,진일보해석료함동수활석교난합성적원인.
A periodic interaction model with different intercalated anions (X=F-, Cl-, Br-, I-, NO-3, OH?) is proposed for the CuZnMgAl quaternary hydrotalcites (CuZnMgAl-X). Based on density functional theory, the CuZnMgAl-X geometry was optimized using the CASTEP program. The distribution of anions in the interlayer, and the supra-molecular interaction between host layer and guest anions were investigated by analyzing binding energies, geometric parameters, Mul iken populations, hydrogen-bonding and densities of states. A decreased electronegativity of interlayer anion caused a transfer of charge from guest anions to host layer and a gradual decrease in the strength of electrostatic interaction and hydrogen bonding. The system band gap narrowed, electrons transferred to higher energy levels more easily, and the overal stability of the system decreased. The Cu dopant caused a deviation in CuZnMgAl-X valence band to high energies. Compared with traditional layered double hydroxides, the band gap narrowed and stability decreased, accounting for the difficulty in preparing copper-containing hydrotalcites.