000127876 001__ 127876 000127876 005__ 20231023120953.0 000127876 0247_ $$2doi$$a10.1021/acsaem.9b00137 000127876 0248_ $$2sideral$$a112692 000127876 037__ $$aART-2019-112692 000127876 041__ $$aeng 000127876 100__ $$aNieto, J. 000127876 245__ $$aEnhanced Chemical and Electrochemical Water Oxidation Catalytic Activity by Hybrid Carbon Nanotube-Based Iridium Catalysts Having Sulfonate-Functionalized NHC ligands 000127876 260__ $$c2019 000127876 5060_ $$aAccess copy available to the general public$$fUnrestricted 000127876 5203_ $$aThe hybrid materials resulting from the covalent attachment of iridium NHC complexes, bearing 3-methyl-imidazol-2-ylidene and 3-(propyl-3-sulfonate)-imidazol-2-ylidene ligands to carbon nanotubes through ester functions, efficiently catalyzed water oxidation under chemical and electrochemical conditions. The hybrid catalyst featuring an NHC ligand with a propyl-sulfonate wingtip has shown an improved catalytic performance compared to that of the unfunctionalized material with TOF50 numbers up to 1140 h(-1) using ammonium cerium(IV) nitrate (CAN) as electron acceptor at [CAN]/[Ir] ratios higher than 2000. The positive effect of the presence of a polar sulfonate group in water oxidation has been also observed in related molecular catalysts with compound [Ir(cod){MeIm(CH2)(3)SO3}] being more active than [IrCl(cod){MeIm(CH2)(3)OH}]. The hybrid catalysts were less active than the molecular catalysts although their productivity has been improved by allowing successive additions of CAN or at least three recycling experiments. The electrochemical water oxidation by CNT-based hybrid materials resulted much more efficient. The positive influence of a watersoluble sulfonate wingtip in the hybrid catalysts has been also identified allowing with TOF values close to 22 000 h(-1) at 1.4 V. The local structure around iridium atoms in the heterogeneous catalysts has been determined by means of EXAFS applied before and after water oxidation reactions. The first coordination shell is similar in both fresh and postcatalytic catalysts but a slightly increase in the oxidation state of iridium atoms is observed what can be correlated to the peaks shifts in the XPS spectra for the oxidized materials. 000127876 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P 000127876 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/ 000127876 590__ $$a4.473$$b2019 000127876 591__ $$aCHEMISTRY, PHYSICAL$$b55 / 159 = 0.346$$c2019$$dQ2$$eT2 000127876 591__ $$aMATERIALS SCIENCE, MULTIDISCIPLINARY$$b85 / 314 = 0.271$$c2019$$dQ2$$eT1 000127876 591__ $$aENERGY & FUELS$$b39 / 112 = 0.348$$c2019$$dQ2$$eT2 000127876 592__ $$a1.495$$b2019 000127876 593__ $$aChemical Engineering (miscellaneous)$$c2019$$dQ1 000127876 593__ $$aElectrical and Electronic Engineering$$c2019$$dQ1 000127876 593__ $$aMaterials Chemistry$$c2019$$dQ1 000127876 593__ $$aEnergy Engineering and Power Technology$$c2019$$dQ1 000127876 593__ $$aElectrochemistry$$c2019$$dQ1 000127876 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion 000127876 700__ $$0(orcid)0000-0002-0545-9107$$aJimenez, M.V.$$uUniversidad de Zaragoza 000127876 700__ $$aAlvarez, P. 000127876 700__ $$aPerez-Mas, A.M. 000127876 700__ $$aGonzalez, Z. 000127876 700__ $$aPereira, R. 000127876 700__ $$0(orcid)0000-0001-6675-7450$$aSanchez-Page, B. 000127876 700__ $$0(orcid)0000-0002-3327-0918$$aPerez-Torrente, J.J.$$uUniversidad de Zaragoza 000127876 700__ $$aBlasco, J. 000127876 700__ $$0(orcid)0000-0002-9029-1977$$aSubias, G.$$uUniversidad de Zaragoza 000127876 700__ $$aBlanco, M. 000127876 700__ $$aMenendez, R. 000127876 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000127876 7102_ $$12003$$2395$$aUniversidad de Zaragoza$$bDpto. Física Materia Condensa.$$cÁrea Física Materia Condensada 000127876 773__ $$g2, 5 (2019), 3283-3296$$pACS app. energy mater.$$tACS applied energy materials$$x2574-0962 000127876 8564_ $$s1559161$$uhttps://zaguan.unizar.es/record/127876/files/texto_completo.pdf$$yPostprint 000127876 8564_ $$s946281$$uhttps://zaguan.unizar.es/record/127876/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint 000127876 909CO $$ooai:zaguan.unizar.es:127876$$particulos$$pdriver 000127876 951__ $$a2023-10-23-11:02:58 000127876 980__ $$aARTICLE