水合pbⅱ cuⅱ和znⅱ离子在高岭石001晶面化学吸附-chemical adsorption of hydrated pb ⅱ cu ⅱ and zn ⅱ ions on kaolinite 001 crystal plane.docx

antibondingstatesistheprimaryorbitalinteractionofPb(II)withoxygen.Surface“Ou”sitewith“up”hydrogenismorefavorableforPb(II)bindingthanthe“Ol”sitewith“lying”hydrogen.Allcomplexesinmono-,bi-andtridentatemodesexhibithemi-directedgeometrywithCNof5,4and5,respectively.Monodentatecomplexof“Ou”siteisfoundthemostenergeticallyfavorable,withbindingenergyofabout20kcal·mol-1higherthanthevaluesofbi-andtridentatecomplexes.ItshouldbethemajorspeciesofPb(II)complexesatrelativelylowpHregion.AtentativecomparisonwithavailableEXAFSresultsforPb(II)adsorptionshowsqualitativeagreementwiththetridentatecomplexof“OuOuOl”siteontwoneighboringAlcenters,whichseemsthelikelytypeathighpHconditions.Thehydrogenbondinginteractionofsurface“Ol”with“H”ofaqualigandsactsasthekeyfactorsindeterminingCNofPb(II)andstabilityofcomplex.Pb(OH)(H2O)5+isfoundthemostprobablespeciesofPb(OH)+inslightlyalkalineaqueoussystemwithholo-directedgeometry.Pb(OH)+canbindwiththekaoliniteAl(o)(001)surfaceinmono-orbidentateway.Allthemono-andbidentatecomplexesexhibitthehemi-directedgeometrywithcoordinationnumberof3to5.Siteof“Ou”ismorefavorableformonodentatecomplexthansiteof“Ol”.Monodentatecomplexationof“Ou”sitewithahighbindingenergyof-43.68kcal·mol-1shouldbethemostpreferredadsorptionmode,whilebidentatecomplexationon“OuOl”siteofsingleAlcenterisalsoprobable.StabilityofadsorptioncomplexisfoundcloselyrelatedtothehydrogenbondinginteractionbetweensurfaceOlandHinaqualigandsofPb(II).Mullikenpopulationanddensityofstates(DOS)analysisshowthatPb6p6dcouplingwiththePb6s–O2pantibondingstatesistheprimaryorbitalinteractionofPb(II)withsurfaceoxygen.Hydrogencomplexationoccupiesamuchlargeproportioninthejointcoordinationstructureofbidentatecomplex,wherethebondingstatefillingpredominatesforPb–Olinteraction.PbCl(H2O)4+isfoundthemostprobablespeciesofPbCl+inthewaterenvironmentwithhemi-directedgeometry.Bothmono-andbidentatePbCl+complexesonkaoliniteAl(o)(001)surfaceexhibitthehemi-directedgeometrywithVcoordinationnumberof3to5.MonodentatecomplexofPb(II)prefersthes