{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,2]],"date-time":"2025-11-02T08:31:51Z","timestamp":1762072311395,"version":"build-2065373602"},"reference-count":45,"publisher":"MDPI AG","issue":"21","license":[{"start":{"date-parts":[[2022,10,29]],"date-time":"2022-10-29T00:00:00Z","timestamp":1667001600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Science and Innovation Ministry (Government of Spain)","award":["PID-2019-104118RB-C21"],"award-info":[{"award-number":["PID-2019-104118RB-C21"]}]},{"name":"FEDER Funds","award":["PID-2019-104118RB-C21"],"award-info":[{"award-number":["PID-2019-104118RB-C21"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["IJMS"],"abstract":"<jats:p>Tb-doped TiO2 (anatase) micro-hollow spheres (HSs) with nano-shells, in the range 0.00\u20133.00 at.% Tb, were successfully synthesized by a simultaneous chemical implantation route of both Ti and Tb cations from chlorides to a poly-styrene (PST)-co-poly-divinyl benzene (PDVB) sacrificial template, followed by controlled hydrolysis and polycondensation reactions. After water addition to the mixture of the precursors with the template, a decrease in the intensity and a shift to lower wavenumbers of the C=O absorption band in the IR spectra can indicate not only the anchoring of Ti and Tb ions to the carbonyl group of the template but also the hydrolysis of the implanted precursors. This latter process can involve a proton attack on the Ti\u2013Cl, Tb\u2013Cl and C=O bonds, the occupation of a vacant site by a water molecule, and then the dissociation of the dangling Ti\u2013Cl, Tb\u2013Cl ligands and C=O bonds. It gives rise to Ti1\u2212xTbx[(OH)4\u2212uClv]@PST\u2013PDVB and Ti1\u2212xTbx[(OH)4\u2212y]@PST\u2013PDVB complexes (x = 0.00, 0.0012, 0.0170 and 0.030). Finally, polycondensation of these species leads to Ti1\u2212xTbxO2\u2212w\u2032@PST\u2013PDVB compounds. After subsequent thermal removal at 550 \u00b0C of the template, the IR bands of the core (template) totally vanished and new bands were observed in the 400\u2013900 cm\u22121 region which can be attributed to the metalloxane bondings (M\u2013O, M\u2019\u2013O, M\u2013O\u2013M, M\u2013O\u2013M\u2019 and\/or M\u2019\u2013O\u2013M\u2019, being M and M\u2019 = Ti and Tb, respectively, i.e., mainly vibration modes of anatase). Then, micron-sized HSs of TiO2 and Tb-doped-TiO2 (anatase) were obtained with nano-shells according to field emission gun scanning electron microscopy (FEG-SEM) and transmission electron microscopy (TEM) observations. Furthermore, X-ray photoelectron spectroscopy (XPS) measurements confirmed the presence of Tb4+ (38.5 and 41.2% for 1.70 and 3.00 at.% Tb, respectively) in addition to Tb3+ in the resulting HSs, with increasing Tb4+ content with both Tb doping and higher calcination temperatures. Then, these HSs can be considered as rare earth (RE) co-doped systems, at least for 1.70 and 3.00 at.% Tb contents being the transition to rutile phase favored by Tb doping for those compositions. Finally, diffusion of Tb from the inner parts to the surface of the HSs with the calcination treatments was also observed by XPS.<\/jats:p>","DOI":"10.3390\/ijms232113162","type":"journal-article","created":{"date-parts":[[2022,10,30]],"date-time":"2022-10-30T07:26:50Z","timestamp":1667114810000},"page":"13162","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Monitoring the Simultaneous Implantation of Ti and Tb Cations to a Sacrificial Template and the Sol-Gel Synthesis of Tb-Doped TiO2 (Anatase) Hollow Spheres and Their Transition to Rutile Phase"],"prefix":"10.3390","volume":"23","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2541-8019","authenticated-orcid":false,"given":"Mar\u00eda Teresa","family":"Colomer","sequence":"first","affiliation":[{"name":"Instituto de Cer\u00e1mica y Vidrio (ICV), Consejo Superior de Investigaciones Cient\u00edficas (CSIC), c\/Kelsen 5, E-28049 Madrid, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9373-2635","authenticated-orcid":false,"given":"Florencia","family":"Vattier","sequence":"additional","affiliation":[{"name":"Instituto de Ciencia de Materiales de Sevilla (ICMS), Consejo Superior de Investigaciones Cient\u00edficas (CSIC)-Universidad de Sevilla, c\/Am\u00e9rico Vespucio 49, E-41092 Sevilla, Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2022,10,29]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Rozman, N., Tobaldi, D.M., Cvelbar, U., Puliyalil, H., Labrincha, J.A., Legat, A., and Sever \u0160kapin, A. (2019). Hydrothermal synthesis of rare-earth modified titania: Influence on phase composition, optical properties, and photocatalytic activity. Materials, 12.","DOI":"10.3390\/ma12050713"},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Thiehmed, Z.A., Altahtamouni, T.M., and Talal, M. (2022). Morphology control of TiO2 nanorods using KBr salt for enhancing the photocatalytic activity of TiO2 and MoS2\/TiO2 heterostructures. Nanomaterials, 12.","DOI":"10.3390\/nano12172904"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"9011","DOI":"10.1016\/j.ceramint.2016.02.159","article-title":"CdS quantum dots sensitized TiO2 nanotubes by matrix assisted pulsed laser evaporation method","volume":"42","author":"Bjelajac","year":"2016","journal-title":"Ceram. Intern."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.apcatb.2016.04.040","article-title":"TiO2 Nanotube arrays: Influence of tube length on the photocatalytic degradation of paraquat","volume":"194","author":"Marien","year":"2016","journal-title":"Appl. Catal. B"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"3005","DOI":"10.1111\/j.1551-2916.2012.05329.x","article-title":"Synthesis and characterization of anatase-structured titania hollow spheres doped with erbium (III)","volume":"95","author":"Borlaf","year":"2012","journal-title":"J. Am. Ceram. Soc."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"5483","DOI":"10.1007\/s10853-013-7342-5","article-title":"Hollow TiO2: Sm3+ spheres with enhanced photoluminescence fabricated by a facile method using polystyrene as template","volume":"48","author":"An","year":"2013","journal-title":"J. Mater. Sci."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"156973","DOI":"10.1016\/j.jallcom.2020.156973","article-title":"Impact of Tb4+ and morphology on the thermal evolution of Tb-doped TiO2 nanostructured hollow spheres and nanoparticles","volume":"853","author":"Colomer","year":"2021","journal-title":"J. Alloys Comp."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"78","DOI":"10.1016\/j.jpcs.2018.10.023","article-title":"Biotemplated synthesis of 3D rare earth-doped TiO2 hollow spheres for photocatalytic application","volume":"126","author":"Bao","year":"2019","journal-title":"J. Phys. Chem. Solids"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"3987","DOI":"10.1002\/adma.200800854","article-title":"Hollow micro-\/nanostructures: Synthesis and applications","volume":"20","author":"Lou","year":"2008","journal-title":"Adv. Mat."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"S32","DOI":"10.1111\/j.1551-2916.2008.02653.x","article-title":"A novel technique for synthesizing nanoshell hollow alumina particles","volume":"92","author":"Wang","year":"2009","journal-title":"J. Am. Ceram. Soc."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"3779","DOI":"10.1016\/j.ceramint.2012.10.217","article-title":"Synthesis and photocatalysis of TiO2 hollow spheres by a facile template-implantation route","volume":"39","author":"Tseng","year":"2013","journal-title":"Ceram. Intern."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1775","DOI":"10.1016\/j.ceramint.2011.01.046","article-title":"Synthesis, microstructure, and photocatalysis of In2O3 hollow particles","volume":"37","author":"Tseng","year":"2011","journal-title":"Ceram. Intern."},{"key":"ref_13","first-page":"532","article-title":"Synthesis, thermal behaviour and luminiscence properties of rare earth-doped titania nanofibers","volume":"126","author":"Caccioti","year":"2011","journal-title":"Mat. Chem. Phys."},{"key":"ref_14","first-page":"354","article-title":"Photocatalytic properties of nanocrystalline TiO2 thin films doped with Tb","volume":"9","author":"Wojcieszak","year":"2011","journal-title":"Cent. Eur. J. Physics"},{"key":"ref_15","unstructured":"Sieradzka, K., and Kaczmarek, D. (2007). Proceedings of the 2007 International Students and Young Scientists Workshop Photonics and Microsystems, IEEE."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"28027","DOI":"10.1021\/acsomega.0c03431","article-title":"Role of rare earth elements and entropy on the anatase-to-rutile phase transformation of TiO2 thin films deposited by ion beam sputtering","volume":"5","author":"Scoca","year":"2020","journal-title":"ACS Omega"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"24","DOI":"10.1016\/j.jorganchem.2019.04.004","article-title":"Cross-linked polystyrene\/titanium tetrachloride as a tightly bound complex catalyzed the modified Mannich reaction for the synthesis of piperidin-4-ones","volume":"892","author":"Rahmatpour","year":"2019","journal-title":"J. Organomet. Chem."},{"key":"ref_18","unstructured":"Pretch, E., Clerc, T., Seibl, J., and Simon, W. (1988). Tablas para la Elucidaci\u00f3n Estructural de Compuestos Org\u00e1nicos por M\u00e9todos Espectrosc\u00f3picos, Alhambra."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"999","DOI":"10.1016\/j.carres.2011.03.020","article-title":"Hydrothermal synthesis, characterization, and KOH activation of carbon spheres from glucose","volume":"346","author":"Li","year":"2011","journal-title":"Carbohydr. Res."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"10980","DOI":"10.1021\/la4021096","article-title":"Chunks of charge: Effects at play in the assembly of macromolecules at fluid surfaces","volume":"35","author":"Robertson","year":"2013","journal-title":"Langmuir"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"223","DOI":"10.1016\/j.jconrel.2004.10.006","article-title":"Incorporation of low molecular weight biocides into polystyrene-divinyl benzene beads with controlled release characteristics","volume":"102","author":"Iconomopoulou","year":"2005","journal-title":"J. Control. Release"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"870","DOI":"10.1088\/0268-1242\/20\/8\/043","article-title":"Dielectric and infrared properties of TiO2 films containing anatase and rutile","volume":"20","author":"Busani","year":"2005","journal-title":"Semicond. Sci. Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"290","DOI":"10.1016\/S0167-577X(97)00181-X","article-title":"Titanium oxide aerogels prepared from titanium metal and hydrogen peroxide","volume":"34","author":"Ayers","year":"1998","journal-title":"Mater. Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"319","DOI":"10.1007\/s00339-019-2622-9","article-title":"Preparation and performance of Fe3O4\/TiO2 nanocomposite with enhanced photo-Fenton activity for photocatalysis by facile hydrothermal method","volume":"125","author":"Vinosel","year":"2019","journal-title":"Appl. Phys. A"},{"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 distribution pore size (IUPAC technical report)","volume":"87","author":"Thommes","year":"2015","journal-title":"Pure Appl. Chem."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"179","DOI":"10.1016\/j.matlet.2007.05.003","article-title":"Enhancement of thermal stability of polydivynil benzene microspheres","volume":"62","author":"Li","year":"2008","journal-title":"Mater. Lett."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3727","DOI":"10.1039\/a805625k","article-title":"Ceria lattice oxygen ion substitution by Cl\u2212 during the reduction of Rh(Cl)\/CeO2 catalysts. Formation and stability of CeOCl","volume":"94","author":"Fajardie","year":"1998","journal-title":"Chem. Soc. Faraday Trans."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"20084","DOI":"10.1039\/C7RA00134G","article-title":"Ligand-free rutile and anatase TiO2 nanocrystals as electron extraction layers for high performance inverted polymer solar cells","volume":"7","author":"Zhu","year":"2017","journal-title":"RSC Adv."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"821","DOI":"10.1038\/nmat3691","article-title":"Electron-pinned defect-dipoles for high-performance colossal permittivity materials","volume":"12","author":"Hu","year":"2013","journal-title":"Nature Mat."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"120","DOI":"10.1002\/sia.1266","article-title":"Influence of the nature of the noble metal (Rh,Pt) on the low-temperature reducibility of a Ce\/Tb mixed oxide with application as TWC component","volume":"34","author":"Blanco","year":"2002","journal-title":"Surf. Interface Anal."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"10234","DOI":"10.1039\/c3ta11610g","article-title":"Bulk transport and oxygen surface exchange of the mixed ionic\u2013electronic conductor Ce1\u2212xTbxO2\u2212\u03b4 (x = 0.1, 0.2, 0.5)","volume":"1","author":"Balaguer","year":"2013","journal-title":"J. Mater. Chem. A"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"10147","DOI":"10.1016\/j.apsusc.2011.07.008","article-title":"Low voltage electron induced cathodoluminescence degradation and surface characterization of Sr3(PO4)2:Tb phosphor","volume":"257","author":"Nagpure","year":"2011","journal-title":"Appl. Surf. Sci."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"3510","DOI":"10.1039\/C5CY01730K","article-title":"In-built Tb4+\/Tb3+ redox centers in terbium-doped bismuth molybdate nanograss for enhanced photocatalytic activity","volume":"6","author":"Li","year":"2016","journal-title":"Catal. Sci. Technol."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"887","DOI":"10.1016\/j.apsusc.2010.07.086","article-title":"Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V.; Cu and Zn","volume":"257","author":"Biesinger","year":"2010","journal-title":"Appl. Surface Sci."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"8278","DOI":"10.1021\/jp068606i","article-title":"The nature of water nucleation sites on TiO2 (110) surfaces revealed by ambient pressure X-ray photoelectron spectroscopy","volume":"111","author":"Ketteler","year":"2007","journal-title":"J. Phys. Chem. C"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"43298","DOI":"10.1038\/srep43298","article-title":"Characterization of photocatalytic TiO2 powder under varied environments using near ambient pressure X-ray photoelectron spectroscopy","volume":"7","author":"Krishnan","year":"2017","journal-title":"Sci. Rep."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"5645","DOI":"10.1023\/A:1018645112465","article-title":"Surface study of titanium-based ceramic electrode material by X-ray photoelectron spectroscopy","volume":"32","author":"Pouilleaue","year":"1997","journal-title":"J. Mat. Sci."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1919","DOI":"10.1111\/j.1151-2916.1999.tb02016.x","article-title":"Enhancing effect of iron chlorides on the anatase-rutile transition in titanium dioxide","volume":"82","author":"Gennari","year":"1999","journal-title":"J. Am. Ceram. Soc."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2267","DOI":"10.1016\/j.jallcom.2017.11.262","article-title":"Evidencing early pyrochlore formation in rare-earth doped TiO2 nanocrystals: Structure sensing via VIS and NIR Er3+ light emission","volume":"735","author":"Camps","year":"2018","journal-title":"J. Alloys Comp."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"8","DOI":"10.1016\/j.matchemphys.2013.11.058","article-title":"Synthesis and photocatalytic activity of Eu3+-doped nanoparticulate TiO2 sols and thermal stability of the resulting xerogels","volume":"144","author":"Borlaf","year":"2014","journal-title":"Mat. Chem. Phys."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"152972","DOI":"10.1016\/j.jallcom.2019.152972","article-title":"Influence of Nd3+ on the structure, thermal evolution and photoluminescence properties of nanoparticulate TiO2 xerogels","volume":"819","author":"Colomer","year":"2020","journal-title":"J. Alloys Comp."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1427","DOI":"10.1016\/0022-1902(70)80629-7","article-title":"Effective ionic radii and crystal chemistry","volume":"32","author":"Shannon","year":"1970","journal-title":"J. Inorg. Nucl. Chem."},{"key":"ref_43","unstructured":"Lee, S. (2012). Oxide Semiconductors for Solar Energy Conversion Titanium Dioxide, CRC Press. [1st ed.]."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"978","DOI":"10.1103\/PhysRev.56.978","article-title":"The Scherrer formula for X-ray particle size determination","volume":"56","author":"Patterson","year":"1939","journal-title":"Phys. Rev."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"437","DOI":"10.1557\/JMR.2000.0067","article-title":"Phase transformation of nanocrystalline anatase-to-rutile via combined interface and surface nucleation","volume":"15","author":"Zhang","year":"2000","journal-title":"J. Mater. Res."}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/21\/13162\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:05:38Z","timestamp":1760144738000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/23\/21\/13162"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,10,29]]},"references-count":45,"journal-issue":{"issue":"21","published-online":{"date-parts":[[2022,11]]}},"alternative-id":["ijms232113162"],"URL":"https:\/\/doi.org\/10.3390\/ijms232113162","relation":{},"ISSN":["1422-0067"],"issn-type":[{"type":"electronic","value":"1422-0067"}],"subject":[],"published":{"date-parts":[[2022,10,29]]}}}