3-氨基-5-巯基-1,2,4-三唑与 Hg(Ⅱ)配位作用的密度泛函理论研究
|
摘要
采用密度泛函理论B3LYP方法研究3-氨基-5-巯基-1,2,4-三唑与Hg(Ⅱ)配位作用特点.计算结果显示,中性配体L的N位点与巯基S位点配位能力近似;而阴离子配体ad-L对Hg(Ⅱ)的配位能力显著增强,与L-N2-Hg及L-S7-Hg配位模式相比,稳定化能分别提高约951.0、960.1 kJ/mol;但阳离子配体p-L配位稳定化能为正.进一步应用DFT化学势和自然键轨道(NBO)分析阴离子配体对Hg(Ⅱ)间存在较强配位作用原因.
The coordination character between 3-amino-5-mercapto-1,2,4-triazole and Hg(Ⅱ) was theoretically studied using density functional theory( DFT) B3 LYP method. The results showed the significantly stronger coordination ability for the ad-L-Hg in comparison to the L-N2-Hg and L-S7-Hg, with apparently higher stabilization energy of about 951.0 and 960.1 kJ/mol, respectively. While negative interaction energy and stabilization energy have been found for the complex with protonation of amino group. Additional analysis was carried out with DFT chemical potential and natural bond orbital NBO for the high reactive ability of ad-L ligand.
The coordination character between 3-amino-5-mercapto-1,2,4-triazole and Hg(Ⅱ) was theoretically studied using density functional theory( DFT) B3 LYP method. The results showed the significantly stronger coordination ability for the ad-L-Hg in comparison to the L-N2-Hg and L-S7-Hg, with apparently higher stabilization energy of about 951.0 and 960.1 kJ/mol, respectively. While negative interaction energy and stabilization energy have been found for the complex with protonation of amino group. Additional analysis was carried out with DFT chemical potential and natural bond orbital NBO for the high reactive ability of ad-L ligand.
引文
[1] Wang X,Zhang F,Qiang T.The research of heavy metal adsorption material.[J].J.Funct.Mater.,2014,45:11001 (in Chinese)
[2] Huang Y,Qiu X,Development and application of the concept of hard-soft-acid-base(HSAB) [J].University Chemistry,2016,31:45 (in Chinese)
[3] Mureseanu M,Reiss A,Cioatera N,et al.Mesoporous silica functionalized with 1-furoyl thiourea urea for Hg(II) adsorption from aqueous media.[J].J.Hazard.Mater.,2010,182:197.
[4] Zhang Y,Xu Q,Zhang S,et al.Preparation of thiol-modified Fe3O4 @SiO2,nanoparticles and their application for gold recovery from dilute solution[J].Sep.Purif.Technol.,2013,116:391.
[5] Xiong C,Jia Q,Chen X,et al.Optimization of polyacrylonitrile-2-aminothiazole resin synthesis,characterization,and its adsorption performance and mechanism for removal of Hg(II) from aqueous solutions[J].Ind.Eng.Chem.Res.,2013,52:4978.
[6] Wang X,Lv P,Zou H,et al.Synthesis of poly(2-aminothiazole) for selective removal of Hg(II) in aqueous solutions[J].Ind.Eng.Chem.Res.,2016,55:4911.
[7] Niu Y,Liu H,Qu R,et al.Preparation and characterization of thiourea-containing silica gel hybrid materials for Hg(II) adsorption[J].Ind.Eng.Chem.Res.,2015,54:1656.
[8] Sun J,Chen Z M,Ge M Y,et al.Selective adsorption of Hg(II) by γ-radiation synthesized silica-graft-vinyl imidazole adsorbent[J].J.Hazard.Mater.,2013,244-245:94.
[9] Fu L,Zhang L,Wang S,et al.Selective adsorption of Ag+,by silica nanoparticles modified with 3-Amino-5-mercapto-1,2,4-triazole from aqueous solutions[J].J.Mol.Liq.,2017,241.
[10] El-Ghaffar M A A,Mohamed M H,Elwakeel K Z.Adsorption of silver(I) on synthetic chelating polymer derived from 3-amino-1,2,4-triazole-5-thiol and glutaraldehyde[J].Chem.Eng.J.,2009,151:30.
[11] He Q,Su G,Li G,et al.Theoretical study on properties of Cu2+ metalated 8- hydroxyquinoline [J].J.At.Mol.Phys.(原子与分子物理学报),2016,33:215 (in Chinese)
[12] He Q,Sun T,Li.DFT theoretical study on coordination character between Mg2+ and Zn2+ and N-Heterocyclic carbene[J].Acta Scientiarum Naturalium:Universitatis Nankaiensis,2015,4:85 (in Chinese)
[13] LI X.Structure and surface-enhanced Raman spectra of glycine dimer adsorbed on surface of silver clusters[J].J.At.Mol.Phys.(原子与分子物理学报,),2016,33:603 (in Chinese)
[14] Rodriguez J I.Indices for predicting the quality of leaving groups.[J].Phys.Chem.Chem.Phys.,2005,7:1918.
[15] Feng X T,Yu J G,Liu R Z,et al.Why iron?a spin-Polarized conceptual density functional theory study on metal-binding specificity of porphyrin[J].J.Phys.Chem.A,2010,114:6342.
[16] Feng X T,Yu J G,Lei M,et al.Toward understanding metal-binding specificity of porphyrin:a conceptual density functional theory study[J].J.Phys.Chem.B,2009,113:13381.
[17] Liu S,Ess D H,Schauer C K.Density functional reactivity theory characterizes charge separation propensity in proton-coupled electron transfer reactions[J].J.Phys.Chem.A,2011,115:4738.
[18] Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 03,Revision B.01.Pittsburgh,PA:Gaussian,Inc.,2003.
[2] Huang Y,Qiu X,Development and application of the concept of hard-soft-acid-base(HSAB) [J].University Chemistry,2016,31:45 (in Chinese)
[3] Mureseanu M,Reiss A,Cioatera N,et al.Mesoporous silica functionalized with 1-furoyl thiourea urea for Hg(II) adsorption from aqueous media.[J].J.Hazard.Mater.,2010,182:197.
[4] Zhang Y,Xu Q,Zhang S,et al.Preparation of thiol-modified Fe3O4 @SiO2,nanoparticles and their application for gold recovery from dilute solution[J].Sep.Purif.Technol.,2013,116:391.
[5] Xiong C,Jia Q,Chen X,et al.Optimization of polyacrylonitrile-2-aminothiazole resin synthesis,characterization,and its adsorption performance and mechanism for removal of Hg(II) from aqueous solutions[J].Ind.Eng.Chem.Res.,2013,52:4978.
[6] Wang X,Lv P,Zou H,et al.Synthesis of poly(2-aminothiazole) for selective removal of Hg(II) in aqueous solutions[J].Ind.Eng.Chem.Res.,2016,55:4911.
[7] Niu Y,Liu H,Qu R,et al.Preparation and characterization of thiourea-containing silica gel hybrid materials for Hg(II) adsorption[J].Ind.Eng.Chem.Res.,2015,54:1656.
[8] Sun J,Chen Z M,Ge M Y,et al.Selective adsorption of Hg(II) by γ-radiation synthesized silica-graft-vinyl imidazole adsorbent[J].J.Hazard.Mater.,2013,244-245:94.
[9] Fu L,Zhang L,Wang S,et al.Selective adsorption of Ag+,by silica nanoparticles modified with 3-Amino-5-mercapto-1,2,4-triazole from aqueous solutions[J].J.Mol.Liq.,2017,241.
[10] El-Ghaffar M A A,Mohamed M H,Elwakeel K Z.Adsorption of silver(I) on synthetic chelating polymer derived from 3-amino-1,2,4-triazole-5-thiol and glutaraldehyde[J].Chem.Eng.J.,2009,151:30.
[11] He Q,Su G,Li G,et al.Theoretical study on properties of Cu2+ metalated 8- hydroxyquinoline [J].J.At.Mol.Phys.(原子与分子物理学报),2016,33:215 (in Chinese)
[12] He Q,Sun T,Li.DFT theoretical study on coordination character between Mg2+ and Zn2+ and N-Heterocyclic carbene[J].Acta Scientiarum Naturalium:Universitatis Nankaiensis,2015,4:85 (in Chinese)
[13] LI X.Structure and surface-enhanced Raman spectra of glycine dimer adsorbed on surface of silver clusters[J].J.At.Mol.Phys.(原子与分子物理学报,),2016,33:603 (in Chinese)
[14] Rodriguez J I.Indices for predicting the quality of leaving groups.[J].Phys.Chem.Chem.Phys.,2005,7:1918.
[15] Feng X T,Yu J G,Liu R Z,et al.Why iron?a spin-Polarized conceptual density functional theory study on metal-binding specificity of porphyrin[J].J.Phys.Chem.A,2010,114:6342.
[16] Feng X T,Yu J G,Lei M,et al.Toward understanding metal-binding specificity of porphyrin:a conceptual density functional theory study[J].J.Phys.Chem.B,2009,113:13381.
[17] Liu S,Ess D H,Schauer C K.Density functional reactivity theory characterizes charge separation propensity in proton-coupled electron transfer reactions[J].J.Phys.Chem.A,2011,115:4738.
[18] Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 03,Revision B.01.Pittsburgh,PA:Gaussian,Inc.,2003.