{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T00:29:03Z","timestamp":1788395343303,"version":"build-2803163510"},"reference-count":38,"publisher":"MDPI AG","issue":"20","license":[{"start":{"date-parts":[[2020,10,14]],"date-time":"2020-10-14T00:00:00Z","timestamp":1602633600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Three different metal oxides (basic MgO, basic-acidic Al2O3 and acidic-basic Nb2O5) characterized by comparable surface areas (MgO\u2014130 m2\/g; Al2O3\u2014172 m2\/g and Nb2O5\u2014123 m2\/g) and pore systems (domination of mesopores with narrow pore size distribution) were modified with tris(2-aminoethyl)amine (TAEA) via two methods: (i) direct anchoring of amine on metal oxide and (ii) anchoring of amine on metal oxide functionalized with (3-chloropropyl)trimethoxysilane. The obtained hybrid materials were characterized in terms of effectiveness of modifier anchoring (elemental analysis), their structural\/textural properties (nitrogen adsorption\/desorption, XRD), acidity\/basicity of support (2-propanol dehydration and dehydrogenation, dehydration and cyclization of 2,5-hexanedione), states of modifier deposited on supports (XPS, FTIR, UV\u2013VIS) and the strength of interaction between the modifier and the support (TG\/DTG). It was evidenced that acidic-basic properties of metal oxides as well as the procedure of modification with TAEA determined the ways of amine anchoring and the strength of its interaction with the support. The obtained hybrid materials were tested in Knoevenagel condensation between furfural and malononitrile. The catalysts based on MgO showed superior activity in this reaction. It was correlated with the way of TAEA anchoring on basic MgO and the strength of modifier anchoring on the support. To the best of our knowledge tris(2-aminoethyl)amine has not been used as a modifier of solid supports for enhancement of the catalyst activity in Knoevenagel condensation.<\/jats:p>","DOI":"10.3390\/molecules25204689","type":"journal-article","created":{"date-parts":[[2020,10,17]],"date-time":"2020-10-17T08:14:50Z","timestamp":1602922490000},"page":"4689","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Tris(2-Aminoethyl)Amine\/Metal Oxides Hybrid Materials\u2014Preparation, Characterization and Catalytic Application"],"prefix":"10.3390","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9075-1198","authenticated-orcid":false,"given":"Katarzyna","family":"Stawicka","sequence":"first","affiliation":[{"name":"Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5050-4042","authenticated-orcid":false,"given":"Maria","family":"Ziolek","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Adam Mickiewicz University in Poznan, Uniwersytetu Poznanskiego 8, 61-614 Poznan, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,10,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"5300","DOI":"10.1021\/acs.jpcb.7b03191","article-title":"Mechanism of the Piperidine-Catalyzed Knoevenagel Condensation Reaction in Methanol: The Role of Iminium and Enolate Ions","volume":"121","author":"Dalessandro","year":"2017","journal-title":"J. Phys. Chem. B"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"45495","DOI":"10.1039\/C7RA06112A","article-title":"Heteropolytungstostannate as a homo- and heterogeneous catalyst for Knoevenagel condensations, selective oxidation of sulfides and oxidative amination of aldehydes","volume":"7","author":"Khoshnavazi","year":"2017","journal-title":"RSC Adv."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1016\/j.cattod.2010.04.031","article-title":"Amino-grafted metallosilicate MCM-41 materials as basic catalysts for eco-friendly processes","volume":"152","author":"Sobczak","year":"2010","journal-title":"Catal. Today"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"681","DOI":"10.1007\/s11244-009-9216-2","article-title":"Applications of Amine-functionalized Mesoporous Silica in Fine Chemical Synthesis","volume":"52","author":"Cheng","year":"2009","journal-title":"Top. Catal."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1016\/j.micromeso.2014.05.018","article-title":"Comparative study of Zr, Nb, Mo containing SBA-15 grafted with amino-organosilanes","volume":"196","author":"Olejniczak","year":"2014","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"64","DOI":"10.1016\/j.micromeso.2017.06.043","article-title":"Cytosine-functionalized SBA-15 mesoporous nanomaterials: Synthesis, characterization and catalytic applications","volume":"253","author":"Rajabi","year":"2017","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_7","doi-asserted-by":"crossref","unstructured":"Park, S.-E., Han, D.-S., Han, S.-C., Jin, M.-J., and Ohsuna, T. (2006). Amino-functionalized SBA-15 type mesoporous silica having nanostructured hexagonal platelet morphology. Chem. Commun., 4131\u20134133.","DOI":"10.1039\/b608463j"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"2762","DOI":"10.1039\/b408022j","article-title":"Preparation of ordered large pore SBA-15 silica functionalized with aminopropyl groups through one-pot synthesis","volume":"2","author":"Wang","year":"2004","journal-title":"Chem. Commun."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Zhu, F., Yang, D., Zhang, F., and Li, H. (2012). Amine-bridged periodic mesoporous organosilica nanospheres as an active and reusable solid base-catalyst for water-medium and solvent-free organic reactions. J. Mol. Catal. A Chem., 387\u2013397.","DOI":"10.1016\/j.molcata.2012.07.015"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1631","DOI":"10.1016\/j.tet.2003.11.086","article-title":"Solid catalysts for the production of fine chemicals: The use of natural phosphate alone and doped base catalysts for the synthesis of unsaturated arylsulfones","volume":"60","author":"Zahouily","year":"2004","journal-title":"Tetrahedron"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"105347","DOI":"10.1039\/C6RA20884C","article-title":"Revival, enhancement and tuning of fluorescence from Coumarin 6: Combination of host\u2013guest chemistry, viscosity and collisional quenching","volume":"6","author":"Banerjee","year":"2016","journal-title":"RSC Adv."},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Lai, S.M., Martin-Aranda, R., and Yeung, K.L. (2003). Knoevenagel condensation reaction in zeolite membrane microreactor. Chem. Commun., 218\u2013219.","DOI":"10.1039\/b209297b"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"648","DOI":"10.1016\/j.ejmech.2015.08.009","article-title":"Unconventional Knoevenagel-type indoles: Synthesis and cell-based studies for the identification of pro-apoptotic agents","volume":"102","author":"Spallarossa","year":"2015","journal-title":"Eur. J. Med. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"5626","DOI":"10.1016\/j.bmc.2010.06.033","article-title":"Synthesis and biological evaluation of arylidene analogues of Meldrum\u2019s acid as a new class of antimalarial and antioxidant agents","volume":"18","author":"Sandhu","year":"2010","journal-title":"Bioorganic Med. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"115","DOI":"10.1016\/j.apcata.2010.04.040","article-title":"The heterogenation of melamine and its catalytic activity","volume":"382","author":"Adam","year":"2010","journal-title":"Appl. Catal. A Gen."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"9781","DOI":"10.1039\/D0DT01621G","article-title":"Calcium and nitrogen species loaded into SBA-15-a promising catalyst tested in Knoevenagel condensation","volume":"49","author":"Kryszak","year":"2020","journal-title":"Dalt. Trans."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"79","DOI":"10.1016\/j.gresc.2020.05.007","article-title":"Primary amine-functionalized mesoporous phenolic resin as an effective and stable solid base catalyst for Knoevenagel reactions in water","volume":"1","author":"Wang","year":"2020","journal-title":"Green Synth. Catal."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"2073","DOI":"10.5012\/bkcs.2011.32.6.2073","article-title":"Effect of diamine in amine-functionalized MIL-101 for Knoevenagel condensation","volume":"32","author":"Palraj","year":"2011","journal-title":"Bull. Korean Chem. Soc."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"288","DOI":"10.1016\/j.micromeso.2019.02.007","article-title":"Impact of Br\u00f8nsted acid sites in MWW zeolites modified with cesium and amine species on Knoevenagel condensation","volume":"280","author":"Grzesinska","year":"2019","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1828","DOI":"10.1039\/c0gc00877j","article-title":"Knoevenagel condensation catalyzed by a tertiary-amine functionalized polyacrylonitrile fiber","volume":"13","author":"Li","year":"2011","journal-title":"Green Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"5122","DOI":"10.1039\/c3dt32495h","article-title":"Amine functionalized K10 montmorillonite: A solid acid\u2013base catalyst for the Knoevenagel condensation reaction","volume":"42","author":"Varadwaj","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"227","DOI":"10.1016\/j.cattod.2019.09.041","article-title":"Highly active hybrid mesoporous silica-supported base organocatalysts for C C bond formation","volume":"345","author":"Erigoni","year":"2020","journal-title":"Catal. Today"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"219","DOI":"10.1023\/A:1018979731407","article-title":"Study of the acidic character of modified metal oxide surfaces using the test of isopropanol decomposition","volume":"43","author":"Gervasini","year":"1997","journal-title":"Catal. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"205","DOI":"10.1016\/0144-2449(90)90047-U","article-title":"Base- and acid-catalysed cyclization of diketones over ZSM-5","volume":"10","author":"Dessau","year":"1990","journal-title":"Zeolites"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1051","DOI":"10.1515\/pac-2014-1117","article-title":"Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)","volume":"87","author":"Thommes","year":"2015","journal-title":"Pure Appl. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2650","DOI":"10.1039\/b921787h","article-title":"One-step ionothermal synthesis of \u03b3-Al2O3 mesoporous nanoflakes at low temperature","volume":"46","author":"Lian","year":"2010","journal-title":"Chem. Commun."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"5445","DOI":"10.1039\/C4NJ01361A","article-title":"Excellent fluoride removal properties of porous hollow MgO microspheres","volume":"38","author":"Li","year":"2014","journal-title":"New J. Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"954","DOI":"10.1590\/S0103-50532009000500022","article-title":"Synthesis, characterization and use of Nb2O5 based catalysts in producing biofuels by transesterification, esterification and pyrolysis","volume":"20","author":"Quirino","year":"2009","journal-title":"J. Braz. Chem. Soc."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"521","DOI":"10.1016\/j.jallcom.2017.04.036","article-title":"Optical properties of MgO and Mg(OH)2 nanostructures synthesized by a chemical precipitation method using impure brine","volume":"711","author":"Yousefi","year":"2017","journal-title":"J. Alloy. Compd."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1016","DOI":"10.13005\/ojc\/340252","article-title":"Synthesis and Structural Profile Analysis of the MgO Nanoparticles Produced Through the Sol-Gel Method Followed by Annealing Process","volume":"34","author":"Sutapa","year":"2018","journal-title":"Orient. J. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Stuart, B. (2004). Infrared Spectroscopy: Fundamentals and Applications, John Wiley & Sons.","DOI":"10.1002\/0470011149"},{"key":"ref_32","first-page":"207","article-title":"Synthesis and characterization of \u03b3-alumina porous nanoparticles from sodium aluminate liquor with two different surfactants","volume":"12","author":"Khazaei","year":"2016","journal-title":"Int. J. Nanosci. Nanotechnol."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"35546","DOI":"10.1039\/C4RA06101B","article-title":"Size-controlled synthesis of mesoporous Nb2O5 microspheres for dye sensitized solar cells","volume":"4","author":"Jin","year":"2014","journal-title":"RSC Adv."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"139","DOI":"10.1016\/j.apcata.2016.10.028","article-title":"Imidazole immobilization in nanopores of silicas and niobiosilicates SBA-15 and MCF\u2014A new concept towards creation of basicity","volume":"531","author":"Kryszak","year":"2017","journal-title":"Appl. Catal. A Gen."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"416","DOI":"10.1016\/j.polymer.2013.09.019","article-title":"Amine-functionalization of glycidyl methacrylate-containing emulsion-templated porous polymers and immobilization of proteinase K for biocatalysis","volume":"55","author":"Kimmins","year":"2014","journal-title":"Polymer (Guildford)"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"629","DOI":"10.1007\/s10934-017-0481-3","article-title":"Synthesis, characterization and catalytic activity of melamine immobilized MCM-41 for condensation reactions","volume":"25","author":"Appaturi","year":"2018","journal-title":"J. Porous Mater."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"43","DOI":"10.1016\/j.micromeso.2017.03.011","article-title":"Catalytic advantages of NH2-modified MIL-53(Al) materials for Knoevenagel condensation reaction","volume":"246","author":"Orcajo","year":"2017","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"67","DOI":"10.1016\/j.micromeso.2017.07.055","article-title":"Highly efficient green mesostructured urea functionalized on SBA-15 catalysts for selective synthesis of benzlidenemalononitrile","volume":"256","author":"Appaturi","year":"2018","journal-title":"Microporous Mesoporous Mater."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/20\/4689\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T10:20:53Z","timestamp":1760178053000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/25\/20\/4689"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,10,14]]},"references-count":38,"journal-issue":{"issue":"20","published-online":{"date-parts":[[2020,10]]}},"alternative-id":["molecules25204689"],"URL":"https:\/\/doi.org\/10.3390\/molecules25204689","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,10,14]]}}}