{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T09:47:24Z","timestamp":1760521644153,"version":"build-2065373602"},"reference-count":52,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2017,4,9]],"date-time":"2017-04-09T00:00:00Z","timestamp":1491696000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia","doi-asserted-by":"publisher","award":["PTDC\/QEQ-ERQ\/1648\/2014","PTDC\/QEQ-QIN\/3967\/2014","UID\/QUI\/00100\/2013"],"award-info":[{"award-number":["PTDC\/QEQ-ERQ\/1648\/2014","PTDC\/QEQ-QIN\/3967\/2014","UID\/QUI\/00100\/2013"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The use of gold as a promotor of alkane hydrocarboxylation is reported for the first time. Cyclohexane hydrocarboxylation to cyclohexanecarboxylic acid (up to 55% yield) with CO, water, and peroxodisulfate in a water\/acetonitrile medium at circa 50 \u00b0C has been achieved in the presence of gold nanoparticles deposited by a colloidal method on a carbon xerogel in its original form (CX), after oxidation with HNO3 (-ox), or after oxidation with HNO3 and subsequent treatment with NaOH (-ox-Na). Au\/CX-ox-Na behaves as re-usable catalyst maintaining its initial activity and selectivity for at least seven consecutive cycles. Green metric values of atom economy or carbon efficiency also attest to the improvement brought by this novel catalytic system to the hydrocarboxylation of cyclohexane.<\/jats:p>","DOI":"10.3390\/molecules22040603","type":"journal-article","created":{"date-parts":[[2017,4,13]],"date-time":"2017-04-13T02:39:17Z","timestamp":1492051157000},"page":"603","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Gold Nanoparticles Deposited on Surface Modified Carbon Xerogels as Reusable Catalysts for Cyclohexane C-H Activation in the Presence of CO and Water"],"prefix":"10.3390","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4323-4328","authenticated-orcid":false,"given":"Ana","family":"Ribeiro","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5403-9352","authenticated-orcid":false,"given":"Lu\u00edsa","family":"Martins","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"},{"name":"Chemical Engineering Department, Instituto Superior de Engenharia de Lisboa, Instituto Polit\u00e9cnico de Lisboa, R. Conselheiro Em\u00eddio Navarro, 1959-007 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9913-4671","authenticated-orcid":false,"given":"S\u00f3nia","family":"Carabineiro","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio de Cat\u00e1lise e Materiais, Laborat\u00f3rio Associado LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0395-8199","authenticated-orcid":false,"given":"Jos\u00e9","family":"Figueiredo","sequence":"additional","affiliation":[{"name":"Laborat\u00f3rio de Cat\u00e1lise e Materiais, Laborat\u00f3rio Associado LSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8323-888X","authenticated-orcid":false,"given":"Armando","family":"Pombeiro","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2017,4,9]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1141","DOI":"10.1246\/cl.1992.1141","article-title":"Transition Metal Catalyzed Acetic Acid Synthesis from Methane and CO","volume":"21","author":"Nishiguchi","year":"1992","journal-title":"Chem. Lett."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"329","DOI":"10.1016\/0022-328X(94)80134-7","article-title":"Palladium(II) and\/or copper(II)-catalyzed carboxylation of small alkanes such as methane and ethane with carbon monoxide","volume":"473","author":"Nakata","year":"1994","journal-title":"J. Organomet. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Derouane, E.D., Haber, J., Lemos, F., Ram\u00f4a Ribeiro, F., and Guinet, M.E. (1998). Catalytic Activation and Functionalisation of Light Alkanes, Kluwer Academic Publ.","DOI":"10.1007\/978-94-017-0982-8"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"633","DOI":"10.1021\/ar000209h","article-title":"Catalytic Functionalization of Arenes and Alkanes via C-H Bond Activation","volume":"34","author":"Jia","year":"2001","journal-title":"Acc. Chem. Res."},{"key":"ref_5","unstructured":"Pombeiro, A.J.L., Fra\u00fasto da Silva, J.J.R., Fujiwara, Y., Silva, J.A.L., Reis, P.M., and Palavra, A.F. (2004). Catalysts and Process for Direct Conversion of Methane into Acetic Acid. (WO 2004\/037416 A3)."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"821","DOI":"10.1002\/anie.200390219","article-title":"Single-Pot Conversion of Methane into Acetic Acid in the Absence of CO and with Vanadium Catalysts Such as Amavadine","volume":"42","author":"Reis","year":"2003","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1016\/j.jcat.2005.09.005","article-title":"Vanadium-catalyzed carboxylation of linear and cyclic C5 and C6 alkanes","volume":"235","author":"Reis","year":"2005","journal-title":"J. Catal."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"10531","DOI":"10.1021\/ja072531u","article-title":"Direct and Remarkably Efficient Conversion of Methane into Acetic Acid Catalyzed by Amavadine and Related Vanadium Complexes. A Synthetic and a Theoretical DFT Mechanistic Study","volume":"129","author":"Kirillova","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1828","DOI":"10.1002\/chem.200700980","article-title":"Amavadin and Other Vanadium Complexes as Remarkably Efficient Catalysts for One-Pot Conversion of Ethane to Propionic and Acetic Acids","volume":"14","author":"Kirillova","year":"2008","journal-title":"Chem. Eur. J."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"2353","DOI":"10.1039\/b900853e","article-title":"Alkanes to carboxylic acids in aqueous medium: Metal-free and metal-promoted highly efficient and mild conversions","volume":"17","author":"Kirillova","year":"2009","journal-title":"Chem. Commun."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"9485","DOI":"10.1002\/chem.201000352","article-title":"Mild, Single-Pot Hydrocarboxylation of Gaseous Alkanes to Carboxylic Acids in Metal-Free and Copper-Promoted Aqueous Systems","volume":"16","author":"Kirillova","year":"2010","journal-title":"Chem. Eur. J."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1002\/adsc.200900660","article-title":"Novel Scorpionate and Pyrazole Dioxovanadium Complexes, Catalysts for Carboxylation and Peroxidative Oxidation of Alkanes","volume":"352","author":"Silva","year":"2010","journal-title":"Adv. Synth. Catal."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"7388","DOI":"10.1021\/ic201396m","article-title":"Metal\u2013Organic Frameworks of Vanadium as Catalysts for Conversion of Methane to Acetic Acid","volume":"50","author":"Phan","year":"2011","journal-title":"Inorg. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"74","DOI":"10.1016\/j.ccr.2014.01.013","article-title":"Tris(pyrazol-1-yl)methane metal complexes for catalytic mild oxidative functionalizations of alkanes, alkenes and ketones","volume":"265","author":"Martins","year":"2014","journal-title":"Coord. Chem. Rev."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Pombeiro, A.J.L. (2014). Toward Functionalization of Alkanes under Environmentally Benign Conditions. Advances in Organometallic Chemistry and Catalysis, The Silver\/Gold Jubilee ICOMC Celebratory Book, J. Wiley & Sons.","DOI":"10.1002\/9781118742952"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2236","DOI":"10.1002\/ejic.201600053","article-title":"Water-Soluble C-Scorpionate Complexes\u2014Catalytic and Biological Applications","volume":"2016","author":"Martins","year":"2016","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Shul\u2019pin, G. (2016). New Trends in Oxidative Functionalization of Carbon-Hydrogen Bonds: A Review. Catalysts, 6.","DOI":"10.3390\/catal6040050"},{"key":"ref_18","unstructured":"Weissermel, W., and Horpe, H.J. (1993). Industrial Organic Chemistry, VCH Press. [2nd ed.]."},{"key":"ref_19","unstructured":"Seidel, A., and Bickford, M. (2004). Encyclopedia of Chemical Technology, Wiley. [5th ed.]."},{"key":"ref_20","unstructured":"Fritz, U. (2002). Ullmann\u2019s Encyclopedia of Industrial Chemistry, Wiley-VCH. [6th ed.]."},{"key":"ref_21","unstructured":"Seidel, A.B.M. (2014). Kirk-Othmer Encyclopedia of Chemical Technology, J. Wiley & Sons."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"2936","DOI":"10.1002\/adsc.200900537","article-title":"Metal-Free and Copper-Promoted Single-Pot Hydrocarboxylation of Cycloalkanes to Carboxylic Acids in Aqueous Medium","volume":"351","author":"Kirillova","year":"2009","journal-title":"Adv. Synth. Catal."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1016\/j.apcata.2005.05.044","article-title":"A golden age of catalysis: A perspective","volume":"291","author":"Hutchings","year":"2005","journal-title":"Appl. Catal. A Gen."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Bond, G.C., Louis, C., and Thompson, D.T. (2006). Catalysis by Gold, Imperial College Press.","DOI":"10.1142\/9781860948954"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1283","DOI":"10.1002\/adsc.200606099","article-title":"Heterogeneous Gold-Catalysed Synthesis of Phenols","volume":"348","author":"Carrettin","year":"2006","journal-title":"Adv. Synth. Catal."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Heiz, U., and Landman, U. (2007). Catalytic Applications for Gold Nanotechnology. Nanocatalysis, Springer.","DOI":"10.1007\/978-3-540-32646-5"},{"key":"ref_27","doi-asserted-by":"crossref","unstructured":"Corti, C., and Holliday, R. (2010). Gold Catalysis. Gold: Science and Applications, CRC Press, Taylor & Francis Group.","DOI":"10.1201\/9781420065268"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"970","DOI":"10.1166\/sam.2011.1227","article-title":"Supported Gold Catalysts for Selective Oxidation of Organics","volume":"3","author":"Wu","year":"2011","journal-title":"Sci. Adv. Mater."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"3056","DOI":"10.1039\/c3cy00552f","article-title":"Homogeneous and heterogenised new gold C-scorpionate complexes as catalysts for cyclohexane oxidation","volume":"3","author":"Martins","year":"2013","journal-title":"Catal. Sci. Technol."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"279","DOI":"10.1016\/j.apcata.2013.07.035","article-title":"Gold nanoparticles supported on carbon materials for cyclohexane oxidation with hydrogen peroxide","volume":"467","author":"Carabineiro","year":"2013","journal-title":"Appl. Catal. A Gen."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"6831","DOI":"10.1002\/ejoc.201001114","article-title":"Mechanistic Dichotomy with Alkynes in the Formal Hydrohydrazination\/Fischer Indolization Tandem Reaction Catalyzed by a Ph3PAuNTf2\/pTSA Binary System","volume":"2010","author":"Patil","year":"2010","journal-title":"Eur. J. Org. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"6918","DOI":"10.1021\/acscatal.5b02090","article-title":"Highly Efficient Gold(I)-Catalyzed Regio- and Stereoselective Hydrocarboxylation of Internal Alkynes","volume":"5","author":"Dupuy","year":"2015","journal-title":"ACS Catal."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"159","DOI":"10.1016\/S0926-860X(98)00113-6","article-title":"A new immobilized Rh(I)-carbonylation catalyst","volume":"172","author":"Protzmann","year":"1998","journal-title":"Appl. Catal. A Gen."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"29","DOI":"10.1016\/j.cattod.2011.08.020","article-title":"Comparison between activated carbon, carbon xerogel and carbon nanotubes for the adsorption of the antibiotic ciprofloxacin","volume":"186","author":"Carabineiro","year":"2012","journal-title":"Catal. Today"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"3847","DOI":"10.1002\/cctc.201300432","article-title":"Heterogenisation of a C-Scorpionate Fe-II Complex on Carbon Materials for Cyclohexane Oxidation with Hydrogen Peroxide","volume":"5","author":"Martins","year":"2013","journal-title":"ChemCatChem"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"2254","DOI":"10.1002\/cctc.201600316","article-title":"Oxidovanadium(V) Complexes Anchored on Carbon Materials as Catalysts for the Oxidation of 1-Phenylethanol","volume":"8","author":"Sutradhar","year":"2016","journal-title":"ChemCatChem"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"4583","DOI":"10.1016\/j.watres.2011.06.008","article-title":"Adsorption of ciprofloxacin on surface-modified carbon materials","volume":"45","author":"Carabineiro","year":"2011","journal-title":"Water Res."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1379","DOI":"10.1016\/S0008-6223(98)00333-9","article-title":"Modification of the surface chemistry of activated carbons","volume":"37","author":"Figueiredo","year":"1999","journal-title":"Carbon"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"4110","DOI":"10.1021\/ie061071v","article-title":"Characterization of Active Sites on Carbon Catalysts","volume":"46","author":"Figueiredo","year":"2007","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1016\/j.cattod.2009.04.010","article-title":"The role of surface chemistry in catalysis with carbons","volume":"150","author":"Figueiredo","year":"2010","journal-title":"Catal. Today"},{"key":"ref_41","unstructured":"Kwiatkowski, J.F. (2011). Surface Chemistry of Activated Carbons. Activated Carbon: Classifications, Properties and Applications, Nova Science Pub Inc."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1016\/j.molcata.2008.10.045","article-title":"Jacobsen catalyst anchored onto modified carbon xerogel as enantioselective heterogeneous catalyst for alkene epoxidation","volume":"305","author":"Maia","year":"2009","journal-title":"J. Mol. Catal. A Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"13045","DOI":"10.1021\/jp400824n","article-title":"Oxygen-Functionalized Highly Mesoporous Carbon Xerogel Based Catalysts for Direct Methanol Fuel Cell Anodes","volume":"117","author":"Alegre","year":"2013","journal-title":"J. Phys. Chem. C"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"7180","DOI":"10.1016\/j.ijhydene.2011.11.022","article-title":"Influence of support\u2019s oxygen functionalization on the activity of Pt\/carbon xerogels catalysts for methanol electro-oxidation","volume":"37","author":"Alegre","year":"2012","journal-title":"Int. J. Hydrogen Energy"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"122","DOI":"10.1016\/j.jcat.2004.01.010","article-title":"Structure sensitivity and kinetics of d-glucose oxidation to d-gluconic acid over carbon-supported gold catalysts","volume":"223","author":"Schimpf","year":"2004","journal-title":"J. Catal."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"420","DOI":"10.1007\/s10562-010-0515-9","article-title":"Selective Oxidation of Glycerol Catalyzed by Rh\/Activated Carbon: Importance of Support Surface Chemistry","volume":"141","author":"Rodrigues","year":"2011","journal-title":"Catal. Lett."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1016\/j.jcat.2011.09.016","article-title":"Gold supported on carbon nanotubes for the selective oxidation of glycerol","volume":"285","author":"Rodrigues","year":"2012","journal-title":"J. Catal."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"93","DOI":"10.1016\/j.chemosphere.2012.11.031","article-title":"Spheres vs. rods: The shape of gold nanoparticles influences aggregation and deposition behavior","volume":"91","author":"Afrooz","year":"2013","journal-title":"Chemosphere"},{"key":"ref_49","unstructured":"Gao, J., and Xu, M. (2007). Metal Nanoparticles of Various Shapes. Advantages of Metal Nanoparticles, ECE-580 Mid-Term Paper, Available online: http:\/\/www.slideserve.com\/nero\/metal-nanoparticles-of-various-shapes."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"343","DOI":"10.1016\/j.apcatb.2011.01.041","article-title":"Influence of support surface basicity and gold particle size on catalytic activity of Au\/\u03b3-AlOOH and Au\/\u03b3-Al2O3 catalyst in aerobic oxidation of \u03b1,\u03c9-diols to lactones","volume":"103","author":"Huang","year":"2011","journal-title":"Appl. Catal. B Environ."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"47740","DOI":"10.1039\/C5RA06496A","article-title":"Effect of alkali and alkaline earth metal ions on benzyl alcohol oxidation activity of titanate nanotube-supported Au catalysts","volume":"5","author":"Nepak","year":"2015","journal-title":"RSC Adv."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"842","DOI":"10.1246\/bcsj.50.842","article-title":"Catalytic Activity of Silver and Gold Metals Doped with Alkali Metals","volume":"50","author":"Shigenobu","year":"1977","journal-title":"Bull. Chem. Soc. Jpn."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/22\/4\/603\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T18:32:17Z","timestamp":1760207537000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/22\/4\/603"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,4,9]]},"references-count":52,"journal-issue":{"issue":"4","published-online":{"date-parts":[[2017,4]]}},"alternative-id":["molecules22040603"],"URL":"https:\/\/doi.org\/10.3390\/molecules22040603","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2017,4,9]]}}}