{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,21]],"date-time":"2026-10-21T23:55:39Z","timestamp":1792626939684,"version":"4.5.0"},"reference-count":52,"publisher":"MDPI AG","issue":"16","license":[{"start":{"date-parts":[[2021,8,12]],"date-time":"2021-08-12T00:00:00Z","timestamp":1628726400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Zhejiang Provincial Natural Science Foundation of China","award":["LQ20B030005"],"award-info":[{"award-number":["LQ20B030005"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>The synthesis of ester compounds is one of the most important chemical processes. In this work, Zn-Mg-Al mixed oxides with different Zn2+\/Mg2+ molar ratios were prepared via co-precipitation method and supported gold nanoclusters to study the direct oxidative esterification of aldehyde and alcohol in the presence of molecular oxygen. Various characterization techniques such as N2-physical adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and CO2 temperature programmed desorption (TPD) were utilized to analyze the structural and electronic properties. Based on the results, the presence of small amounts of Zn2+ ions (~5 wt.%) provoked a remarkable modification of the binary Mg-Al system, which enhanced the interaction between gold with the support and reduced the particle size of gold. For oxidative esterification reaction, the Au25\/Zn0.05MgAl-400 catalyst showed the best performance, with the highest turnover frequency (TOF) of 1933 h\u22121. The active center was believed to be located at the interface between metallic gold with the support, where basic sites contribute a lot to transformation of the substrate.<\/jats:p>","DOI":"10.3390\/ijms22168668","type":"journal-article","created":{"date-parts":[[2021,8,12]],"date-time":"2021-08-12T10:54:41Z","timestamp":1628765681000},"page":"8668","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Zn Promoted Mg-Al Mixed Oxides-Supported Gold Nanoclusters for Direct Oxidative Esterification of Aldehyde to Ester"],"prefix":"10.3390","volume":"22","author":[{"given":"Jie","family":"Li","sequence":"first","affiliation":[{"name":"Hangzhou Institute of Advanced Studies, Zhejiang Normal University, 1108 Gengwen Road, Hangzhou 311231, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shiyi","family":"Wang","sequence":"additional","affiliation":[{"name":"Hangzhou Institute of Advanced Studies, Zhejiang Normal University, 1108 Gengwen Road, Hangzhou 311231, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huayin","family":"Li","sequence":"additional","affiliation":[{"name":"Hangzhou Institute of Advanced Studies, Zhejiang Normal University, 1108 Gengwen Road, Hangzhou 311231, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3337-897X","authenticated-orcid":false,"given":"Yuan","family":"Tan","sequence":"additional","affiliation":[{"name":"Hangzhou Institute of Advanced Studies, Zhejiang Normal University, 1108 Gengwen Road, Hangzhou 311231, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yunjie","family":"Ding","sequence":"additional","affiliation":[{"name":"Hangzhou Institute of Advanced Studies, Zhejiang Normal University, 1108 Gengwen Road, Hangzhou 311231, China"},{"name":"Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China"},{"name":"The State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2021,8,12]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"15618","DOI":"10.1002\/chem.201403786","article-title":"Efficient and Simple Approaches Towards Direct Oxidative Esterification of Alcohols","volume":"20","author":"Ray","year":"2014","journal-title":"Chem. Eur. J."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"9472","DOI":"10.1039\/C8OB02539H","article-title":"Efficient synthesis of esters through oxone-catalyzed dehydrogenation of carboxylic acids and alcohols","volume":"16","author":"Hou","year":"2018","journal-title":"Org. Biomol. Chem."},{"key":"ref_3","first-page":"3461","article-title":"Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry","volume":"33","author":"Jayachitra","year":"2003","journal-title":"Synth. Commun."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"154","DOI":"10.1002\/adsc.201500912","article-title":"Metal-Free Oxidative Cross Esterification of Alcohols via Acyl Chloride Formation","volume":"358","author":"Gaspa","year":"2016","journal-title":"Adv. Synth. Catal."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"4537","DOI":"10.1016\/S0040-4039(00)84997-7","article-title":"KMnO4 revisited: Oxidation of aldehydes to carboxylic acids in the-butyl alcohol-aqueous NaH2PO4 system","volume":"27","author":"Abiko","year":"1986","journal-title":"Tetrahedron Lett."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"3235","DOI":"10.1016\/S0040-4039(00)95480-7","article-title":"ChemInform Abstract: A New Method for the Conversion of Aldehydes to Methyl Esters Using Pyridinium Dichromate and Methanol in Dimethylformamide","volume":"28","author":"Just","year":"1987","journal-title":"Tetrahedron Lett."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"3397","DOI":"10.1016\/j.tetlet.2012.04.111","article-title":"Zinc-catalyzed oxidative esterification of aromatic aldehydes","volume":"53","author":"Wu","year":"2012","journal-title":"Tetrahedron Lett."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"5072","DOI":"10.1021\/ol402428e","article-title":"Aerobic Oxidation of Diverse Primary Alcohols to Methyl Esters with a Readily Accessible Heterogeneous Pd\/Bi\/Te Catalyst","volume":"15","author":"Powell","year":"2013","journal-title":"Org. Lett."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"5662","DOI":"10.1002\/anie.201201960","article-title":"Covalently Bound Benzyl Ligand Promotes Selective Palladium Catalyzed Oxidative Esterification of Aldehydes with Alcohols","volume":"51","author":"Liu","year":"2012","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"48","DOI":"10.1016\/j.catcom.2016.10.015","article-title":"Pd(OAc)2\/dppp, an efficient catalytic system for the oxidative esterification of benzaldehyde using organic halides as oxidants","volume":"89","author":"Biajoli","year":"2017","journal-title":"Catal. Commun."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1038","DOI":"10.1021\/acscatal.7b02886","article-title":"Mechanistic Insights into Aerobic Oxidative Methyl Esterification of Primary Alcohols with Heterogeneous PdBiTe Catalysts","volume":"8","author":"Mannel","year":"2018","journal-title":"ACS Catal."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"3050","DOI":"10.1039\/C8GC01393D","article-title":"Aerobic oxidative esterification of 5-hydroxymethylfurfural to dimethyl furan-2, 5-dicarboxylate by using homogeneous and heterogeneous PdCoBi\/C catalysts under atmospheric oxygen","volume":"20","author":"Li","year":"2018","journal-title":"Green Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"2215","DOI":"10.1002\/adsc.201801595","article-title":"Recent Progress in Catalytic Oxidative Transformations of Alcohols by Supported Gold Nanoparticles","volume":"361","author":"Hui","year":"2019","journal-title":"Adv. Synth. Catal."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"80","DOI":"10.1016\/j.apcata.2018.09.004","article-title":"Fabrication of supported Au-CuOx nanohybrids by reduction-oxidation strategy for efficient oxidative esterification of 5-hydroxymethyl-2-furfural into dimethyl furan-2,5-dicarboxylate","volume":"567","author":"Du","year":"2018","journal-title":"Appl. Catal. A"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"117169","DOI":"10.1016\/j.apcata.2019.117169","article-title":"Oxidative esterification of aliphatic aldehydes and alcohols with ethanol over gold nanoparticle catalysts in batch and continuous flow reactors","volume":"585","author":"Taketoshi","year":"2019","journal-title":"Appl. Catal."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1016\/j.catcom.2019.03.002","article-title":"A sustainable oxidative esterification of thiols with alcohols by a cobalt nanocatalyst supported on doped carbon","volume":"124","author":"Zuo","year":"2019","journal-title":"Catal. Commun."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"338","DOI":"10.1016\/j.jiec.2018.10.034","article-title":"Hydroxyapatite supported gold nanocatalyst for base-free oxidative esterification of 5-hydroxymethyl-2-furfural to 2,5-furan dimethylcarboxylate with air as oxidant","volume":"70","author":"Mishra","year":"2019","journal-title":"J. Ind. Eng. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"111265","DOI":"10.1016\/j.mcat.2020.111265","article-title":"Study of the oxidative esterification of furfural catalyzed by Au25(glutathione)18 nanocluster deposited on zirconia","volume":"499","author":"Shahin","year":"2021","journal-title":"Mol. Catal."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Liu, L., Li, H., Tan, Y., Chen, X., Lin, R., Yang, W., Huang, C., Wang, S., Wang, X., and Liu, X. (2020). Metal-support synergy of supported gold nanoclusters in selective oxidation of alcohols. Catalysts, 10.","DOI":"10.3390\/catal10010107"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1523","DOI":"10.1007\/s10904-019-01116-0","article-title":"Phosphotungstic Acid Supported on MgAl2O4 Nanoparticles as an Efficient and Reusable Nanocatalyst for Benzylic Alcohols Oxidation with Hydrogen Peroxide","volume":"29","author":"Hajavazzade","year":"2019","journal-title":"J. Inorg. Organomet. Polym. Mater."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"85","DOI":"10.1016\/j.apcata.2017.02.020","article-title":"Reconstructed Mg-Al hydrotalcites prepared by using different rehydration and drying time: Physico-chemical properties and catalytic performance in aldol condensation","volume":"536","author":"Kikhtyanin","year":"2017","journal-title":"Appl. Catal. A"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"310","DOI":"10.1016\/S1872-2067(12)60738-4","article-title":"Transesterification of glycerol with dimethyl carbonate over Mg-Al hydrotalcites","volume":"35","author":"Zheng","year":"2014","journal-title":"Chin. J. Catal."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1614","DOI":"10.1016\/j.jclepro.2018.11.150","article-title":"Tunable copper-hydrotalcite derived mixed oxides for sustainable ethanol condensation to n-butanol in liquid phase","volume":"209","author":"Benito","year":"2019","journal-title":"J. Clean. Prod."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"15119","DOI":"10.1021\/acssuschemeng.8b03589","article-title":"A Pinch of Salt Improves n-Butanol Selectivity in the Guerbet Condensation of Ethanol over Cu-Doped Mg\/Al Oxides","volume":"6","author":"Barrett","year":"2018","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_25","first-page":"628","article-title":"Tuning the acidic\u2013basic properties by Zn substitution in Mg\u2013Al hydrotalcites as optimal catalysts for the aldol condensation reaction","volume":"52","author":"Verberckmoes","year":"2016","journal-title":"J. Mater. Sci."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"111","DOI":"10.1016\/j.clay.2007.12.006","article-title":"Influence of acid-base properties of ZnMgAl-mixed oxides for the synthesis of 1-methoxy-2-propanol","volume":"42","author":"Cheng","year":"2008","journal-title":"Appl. Clay Sci."},{"key":"ref_27","first-page":"36","article-title":"Sorption-enhanced steam reforming of ethanol on NiMgAl multifunctional materials: Experimental and numerical investigation","volume":"231","author":"Wu","year":"2013","journal-title":"Chem. Eur. J."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"83","DOI":"10.1016\/j.apcata.2011.06.017","article-title":"The activity of yttrium-modified Mg, Al hydrotalcites in the epoxidation of styrene with hydrogen peroxide","volume":"403","author":"Pavel","year":"2011","journal-title":"Appl. Catal. A"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1016\/j.apcata.2016.05.015","article-title":"Transesterification of rapeseed oil to biodiesel over Zr-dopped MgAl hydrotalcites","volume":"524","author":"Nowicki","year":"2016","journal-title":"Appl. Catal. A"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2709","DOI":"10.1002\/anie.201610736","article-title":"ZnAl-Hydrotalcite-Supported Au25 Nanoclusters as Precatalysts for Chemoselective Hydrogenation of 3-Nitrostyrene","volume":"56","author":"Tan","year":"2017","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Li, H., Tan, Y., Chen, X., Yang, W., Huang, C., Li, J., and Ding, Y. (2021). Efficient Synthesis of Methyl Methacrylate by One Step Oxidative Esterification over Zn-Al-Mixed Oxides Supported Gold Nanocatalysts. Catalysts, 11.","DOI":"10.3390\/catal11020162"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"110731","DOI":"10.1016\/j.micromeso.2020.110731","article-title":"Copper functionalized solid base prepared by potassium modification of N-doped carbons to promote the conversion of ethanol to butanol","volume":"311","author":"Jiang","year":"2021","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"52","DOI":"10.1016\/j.clay.2012.03.006","article-title":"Acido-basic and catalytic properties of transition-metal containing Mg\u2013Al hydrotalcites and their corresponding mixed oxides","volume":"61","author":"Pavel","year":"2012","journal-title":"Appl. Clay Sci."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"195","DOI":"10.1016\/j.colsurfa.2012.10.014","article-title":"Preparation of nanostructured microspheres of Zn\u2013Mg\u2013Al layered double hydroxides with high adsorption property","volume":"415","author":"Zheng","year":"2012","journal-title":"Colloids Surf. A Physicochem. Eng. Asp."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"751","DOI":"10.1107\/S0567739476001551","article-title":"Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides","volume":"32","author":"Shannon","year":"1976","journal-title":"Acta Cryst."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"330","DOI":"10.1016\/j.apcatb.2009.03.019","article-title":"Adsorption and photocatalytic degradation of phenol and 2,4 dichlorophenoxiacetic acid by Mg\u2013Zn\u2013Al layered double hydroxides","volume":"90","author":"Valente","year":"2009","journal-title":"Appl. Catal. B"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"470","DOI":"10.1016\/S1872-2067(20)63678-6","article-title":"Producing of cinnamyl alcohol from cinnamaldehyde over supported gold nanocatalyst","volume":"42","author":"Tan","year":"2021","journal-title":"Chin. J. Catal."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"51","DOI":"10.1016\/j.catcom.2019.03.002","article-title":"One step oxidative esterification of methacrolein with methanol over AuCeO2\/\u03b3-Al2O3 catalysts","volume":"124","author":"Zuo","year":"2019","journal-title":"Catal. Commun."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"13419","DOI":"10.1002\/slct.201803183","article-title":"Photocatalytic Performance on Visible Light Induced ZnS QDs-MgAl Layered Double Hydroxides Hybrids for Methylene Blue Dye Degradation","volume":"3","author":"Bhuvaneswari","year":"2018","journal-title":"ChemistrySelect"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"6285","DOI":"10.1039\/D0CY00980F","article-title":"Dynamic charge transfer through Fermi level equilibration in the p-CuFe2O4\/n-NiAl LDH interface towards photocatalytic application","volume":"10","author":"Das","year":"2020","journal-title":"Catal. Sci. Technol."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"1230","DOI":"10.1002\/cctc.201601560","article-title":"Oxidative Esterification of Methacrolein to Methyl Methacrylate over Gold Nanoparticles on Hydroxyapatite","volume":"9","author":"Gao","year":"2017","journal-title":"ChemCatChem"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"19397","DOI":"10.1021\/acs.iecr.9b02571","article-title":"Nano-Au\/MCeOx Catalysts for the Direct Oxidative Esterification of Methylacrolein to Methyl Esters","volume":"58","author":"Tian","year":"2019","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"1902","DOI":"10.1039\/C9CY02523E","article-title":"Ni-based catalysts supported on Mg-Al hydrotalcites with different morphologies for CO2 methanation: Exploring the effect of metal-support interaction","volume":"10","author":"Ren","year":"2020","journal-title":"Catal. Sci. Technol."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/j.cattod.2015.03.017","article-title":"Ni-containing Ce-promoted hydrotalcite derived materials as catalysts for methane reforming with carbon dioxide at low temperature-On the effect of basicity","volume":"257","author":"Radlik","year":"2015","journal-title":"Catal. Today"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.ccr.2016.05.003","article-title":"Recent advances in the synthesis and catalytic applications of ligand-protected, atomically precise metal nanoclusters","volume":"322","author":"Fang","year":"2016","journal-title":"Coord. Chem. Rev."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"380","DOI":"10.1246\/cl.131232","article-title":"Size- and Structure-specificity in Catalysis by Gold Clusters","volume":"43","author":"Taketoshi","year":"2014","journal-title":"Chem. Lett."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1016\/j.cattod.2013.12.012","article-title":"Magnesia-supported gold nanoparticles as efficient catalysts for oxidative esterification of aldehydes or alcohols with methanol to methyl esters","volume":"233","author":"Wan","year":"2014","journal-title":"Catal. Today"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"804","DOI":"10.1016\/j.cattod.2019.04.021","article-title":"NiAu single atom alloys for the selective oxidation of methacrolein with methanol to methyl methacrylate","volume":"355","author":"Trimpalis","year":"2020","journal-title":"Catal. Today"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"1960","DOI":"10.1002\/cctc.201601688","article-title":"Oxidative Esterification of Methacrolein to Methyl Methacrylate over Supported Gold Catalysts Prepared by Colloid Deposition","volume":"9","author":"Li","year":"2017","journal-title":"ChemCatChem"},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"4066","DOI":"10.1021\/jp027596s","article-title":"Interaction of O2 with Gold Clusters: Molecular and Dissociative Adsorption","volume":"107","author":"Yoon","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"981","DOI":"10.1038\/nature07194","article-title":"Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters","volume":"454","author":"Turner","year":"2008","journal-title":"Nature"},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"61","DOI":"10.1038\/nchem.467","article-title":"Vapour-phase gold-surface-mediated coupling of aldehydes with methanol","volume":"2","author":"Xu","year":"2010","journal-title":"Nat. Chem."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/22\/16\/8668\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:44:46Z","timestamp":1760165086000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/22\/16\/8668"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,8,12]]},"references-count":52,"journal-issue":{"issue":"16","published-online":{"date-parts":[[2021,8]]}},"alternative-id":["ijms22168668"],"URL":"https:\/\/doi.org\/10.3390\/ijms22168668","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,8,12]]}}}