000056099 001__ 56099
000056099 005__ 20200221144333.0
000056099 0247_ $$2doi$$a10.1039/c5nj02773j
000056099 0248_ $$2sideral$$a93688
000056099 037__ $$aART-2016-93688
000056099 041__ $$aeng
000056099 100__ $$aLang, Z.
000056099 245__ $$aOn the formation of gold nanoparticles from [AuIIICl4]- and a non-classical reduced polyoxomolybdate as an electron source: A quantum mechanical modelling and experimental study
000056099 260__ $$c2016
000056099 5060_ $$aAccess copy available to the general public$$fUnrestricted
000056099 5203_ $$aPolyoxometalate (POM)-mediated reduction and nucleation mechanisms in nanoparticle (NP) syntheses are still largely unknown. We carried out comprehensive theoretical analysis using density functional theory (DFT) to gain insight into the molecular and electronic changes that occur during the reduction of HAuIIICl4 with the Kabanos-type polyoxomolybdate, Na{(MoV2O4)3(µ2-O)3(µ2-SO3)3(µ6-SO3)}2]15-. In the system presented herein the electrons are supplied by the POM, making the computational thermodynamic analysis more feasible. Our results reveal that this particular POM is a multi-electron source and the proton-coupled electron transfer (PCET) greatly promotes the reduction process. Based on the energy and molecular orbital studies of the intermediate species the reduction of AuIII to AuI is shown to be thermodynamically favourable, and a low HOMO-LUMO gap of the POM-Au superstructure is advantageous for electron transfer. By modelling the reduction of three couples of AuIII ¿ AuI by the same POM unit, it is proposed that the reduced polyoxomolybdate is finally fully oxidised. The subjacent idea of using the Kabanos POM was confirmed by comprehensive experimental characterisation of POM-stabilised gold nanoparticles (AuNPs@POM). Present theoretical analysis suggests that protons have a significant influence on the final AuI to Au0 reduction step that ultimately leads to colloidal AuNPs@POM.
000056099 536__ $$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-29054$$9info:eu-repo/grantAgreement/EC/FP7/239931/EU/Multifunctional Magnetic Nanoparticles: Towards Smart Drugs Design/NANOPUZZLE
000056099 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttp://creativecommons.org/licenses/by-nc/3.0/es/
000056099 590__ $$a3.269$$b2016
000056099 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b52 / 166 = 0.313$$c2016$$dQ2$$eT1
000056099 592__ $$a0.868$$b2016
000056099 593__ $$aChemistry (miscellaneous)$$c2016$$dQ1
000056099 593__ $$aMaterials Chemistry$$c2016$$dQ1
000056099 593__ $$aCatalysis$$c2016$$dQ2
000056099 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000056099 700__ $$aMaicas Gabas, I.
000056099 700__ $$aLópez, X.
000056099 700__ $$aClotet, A.
000056099 700__ $$0(orcid)0000-0003-1081-8482$$aMartínez de la Fuente, J.$$uUniversidad de Zaragoza
000056099 700__ $$aMitchell, S.G.
000056099 700__ $$aPoblet, J.M.
000056099 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000056099 773__ $$g40, 2 (2016), 1029-1038$$pNew j. chem.$$tNEW JOURNAL OF CHEMISTRY$$x1144-0546
000056099 8564_ $$s2687577$$uhttps://zaguan.unizar.es/record/56099/files/texto_completo.pdf$$yVersión publicada
000056099 8564_ $$s112697$$uhttps://zaguan.unizar.es/record/56099/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000056099 909CO $$ooai:zaguan.unizar.es:56099$$particulos$$pdriver
000056099 951__ $$a2020-02-21-13:46:22
000056099 980__ $$aARTICLE