{"id":55547,"date":"2022-12-01T15:13:10","date_gmt":"2022-12-01T13:13:10","guid":{"rendered":"https:\/\/www.iemn.fr\/?p=55547"},"modified":"2022-12-01T15:13:10","modified_gmt":"2022-12-01T13:13:10","slug":"these-f-venel-stabilite-en-presence-deau-des-materiaux-hybrides-microporeux-de-type-metal-organic-frameworks-apport-de-la-rmn-des-solides-2","status":"publish","type":"post","link":"https:\/\/www.iemn.fr\/en\/these\/these-2021\/these-f-venel-stabilite-en-presence-deau-des-materiaux-hybrides-microporeux-de-type-metal-organic-frameworks-apport-de-la-rmn-des-solides-2.html","title":{"rendered":"THESE : F.VENEL &#8211; Stabilit\u00e9 en pr\u00e9sence d&rsquo;eau des mat\u00e9riaux hybrides microporeux de type metal-organic frameworks : apport de la RMN des solides"},"content":{"rendered":"<div id='layer_slider_1'  class='avia-layerslider main_color avia-shadow  avia-builder-el-0  el_before_av_heading  avia-builder-el-first  container_wrap sidebar_right'  style='height: 261px;'  ><div id=\"layerslider_58_bsr5t2wb58fq\" data-ls-slug=\"homepageslider\" class=\"ls-wp-container fitvidsignore ls-selectable\" style=\"width:1140px;height:260px;margin:0 auto;margin-bottom: 0px;\"><div class=\"ls-slide\" data-ls=\"duration:6000;transition2d:5;\"><img loading=\"lazy\" decoding=\"async\" width=\"2600\" height=\"270\" src=\"https:\/\/www.iemn.fr\/wp-content\/uploads\/2019\/01\/sliders_news1.jpg\" class=\"ls-bg\" alt=\"\" srcset=\"https:\/\/www.iemn.fr\/wp-content\/uploads\/2019\/01\/sliders_news1.jpg 2600w, https:\/\/www.iemn.fr\/wp-content\/uploads\/2019\/01\/sliders_news1-300x31.jpg 300w, https:\/\/www.iemn.fr\/wp-content\/uploads\/2019\/01\/sliders_news1-768x80.jpg 768w, https:\/\/www.iemn.fr\/wp-content\/uploads\/2019\/01\/sliders_news1-1030x107.jpg 1030w, https:\/\/www.iemn.fr\/wp-content\/uploads\/2019\/01\/sliders_news1-1500x156.jpg 1500w, https:\/\/www.iemn.fr\/wp-content\/uploads\/2019\/01\/sliders_news1-705x73.jpg 705w\" sizes=\"auto, (max-width: 2600px) 100vw, 2600px\" \/><ls-layer style=\"font-size:14px;text-align:left;font-style:normal;text-decoration:none;text-transform:none;font-weight:700;letter-spacing:0px;border-style:solid;border-color:#000;background-position:0% 0%;background-repeat:no-repeat;width:180px;height:30px;left:0px;top:231px;line-height:32px;color:#ffffff;border-radius:6px 6px 6px 6px;padding-left:50px;background-color:rgba(0, 0, 0, 0.57);\" class=\"ls-l ls-ib-icon ls-text-layer\" data-ls=\"minfontsize:0;minmobilefontsize:0;\"><i class=\"fa fa-quote-right\" style=\"color:#ffffff;margin-right:0.8em;font-size:1em;transform:translateY( -0.125em );\"><\/i>ACTUALITES<\/ls-layer><\/div><\/div><\/div><div id='after_layer_slider_1'  class='main_color av_default_container_wrap container_wrap sidebar_right'  ><div class='container av-section-cont-open' ><div class='template-page content  av-content-small alpha units'><div class='post-entry post-entry-type-page post-entry-55547'><div class='entry-content-wrapper clearfix'>\n\n<style type=\"text\/css\" data-created_by=\"avia_inline_auto\" id=\"style-css-av-lb53j9sz-0af640042c08317a4761f303f1a3f036\">\n#top .av-special-heading.av-lb53j9sz-0af640042c08317a4761f303f1a3f036{\nmargin:0 0 10px 0;\npadding-bottom:4px;\n}\nbody .av-special-heading.av-lb53j9sz-0af640042c08317a4761f303f1a3f036 .av-special-heading-tag .heading-char{\nfont-size:25px;\n}\n.av-special-heading.av-lb53j9sz-0af640042c08317a4761f303f1a3f036 .av-subheading{\nfont-size:15px;\n}\n<\/style>\n<div  class='av-special-heading av-lb53j9sz-0af640042c08317a4761f303f1a3f036 av-special-heading-h2  avia-builder-el-1  el_after_av_layerslider  el_before_av_hr  avia-builder-el-first'><h2 class='av-special-heading-tag'  itemprop=\"headline\"  >THESE : F.VENEL \u2013 Stabilit\u00e9 en pr\u00e9sence d\u2019eau des mat\u00e9riaux hybrides microporeux de type metal-organic frameworks : apport de la RMN des solides <\/h2><div class=\"special-heading-border\"><div class=\"special-heading-inner-border\"><\/div><\/div><\/div>\n\n<style type=\"text\/css\" data-created_by=\"avia_inline_auto\" id=\"style-css-av-18u73nj-dad6a947580930e400fc42ba200e80f1\">\n#top .hr.av-18u73nj-dad6a947580930e400fc42ba200e80f1{\nmargin-top:5px;\nmargin-bottom:5px;\n}\n.hr.av-18u73nj-dad6a947580930e400fc42ba200e80f1 .hr-inner{\nwidth:100%;\n}\n<\/style>\n<div  class='hr av-18u73nj-dad6a947580930e400fc42ba200e80f1 hr-custom  avia-builder-el-2  el_after_av_heading  el_before_av_textblock  hr-left hr-icon-no'><span class='hr-inner inner-border-av-border-thin'><span class=\"hr-inner-style\"><\/span><\/span><\/div>\n<section  class='av_textblock_section av-jriy64i8-2f4600354c0449b610997916bbd9b6bc'   itemscope=\"itemscope\" itemtype=\"https:\/\/schema.org\/BlogPosting\" itemprop=\"blogPost\" ><div class='avia_textblock'  itemprop=\"text\" >\n<style type=\"text\/css\" data-created_by=\"avia_inline_auto\" id=\"style-css-av-13ewzjw-68e036126b913e5028f77311dc66b825\">\n.av_font_icon.av-13ewzjw-68e036126b913e5028f77311dc66b825{\ncolor:#bfbfbf;\nborder-color:#bfbfbf;\n}\n.av_font_icon.av-13ewzjw-68e036126b913e5028f77311dc66b825 .av-icon-char{\nfont-size:60px;\nline-height:60px;\n}\n<\/style>\n<span  class='av_font_icon av-13ewzjw-68e036126b913e5028f77311dc66b825 avia_animate_when_visible av-icon-style- avia-icon-pos-left avia-icon-animate'><span class='av-icon-char' aria-hidden='true' data-av_icon='\ue8c9' data-av_iconfont='entypo-fontello' ><\/span><\/span>\n<p><strong>F.VENEL<\/strong><\/p>\n<p>Soutenance : <strong><span class=\"titre\">6 Octobre<\/span> <span class=\"annee_parution\">2021<\/span><br \/>\n<\/strong><span class=\"titre\">Th\u00e8se de doctorat en Chimie des materiaux, Universit\u00e9 de Lille, ED SMRE, <\/span><\/p>\n<\/div><\/section>\n<section  class='av_textblock_section av-jtefqx33-628129dba2299b2ecd65ebfc92eac29d'   itemscope=\"itemscope\" itemtype=\"https:\/\/schema.org\/BlogPosting\" itemprop=\"blogPost\" ><div class='avia_textblock'  itemprop=\"text\" ><div  class='hr av-kjh3zw-4dff888f744b728a1aca9b3a0971493a hr-default  avia-builder-el-6  avia-builder-el-no-sibling'><span class='hr-inner'><span class=\"hr-inner-style\"><\/span><\/span><\/div>\n<h5>Summary:<\/h5>\n<p>Les Metal-Organic Frameworks (MOF) sont des mat\u00e9riaux hybrides poreux cristallis\u00e9s constitu\u00e9s de clusters inorganiques li\u00e9s les uns aux autres par des ligands organiques. La structure de ces compos\u00e9s offre une porosit\u00e9 tr\u00e8s importante et des surfaces sp\u00e9cifiques \u00e9lev\u00e9es (jusqu\u2019\u00e0 plusieurs milliers de m\u00b2\/g). Mais leur utilisation dans des proc\u00e9d\u00e9s industriels reste peu d\u00e9velopp\u00e9e, notamment \u00e0 cause d\u2019un manque de connaissance sur leur r\u00e9activit\u00e9 vis-\u00e0-vis de l\u2019eau. En cours de cette th\u00e8se, diff\u00e9rentes techniques ont \u00e9t\u00e9 utilis\u00e9es afin d\u2019\u00e9tudier les modifications structurales pouvant intervenir sur l\u2019UiO-66(Zr) en pr\u00e9sence de vapeur d\u2019eau : la diffraction des rayons X, l\u2019infrarouge, la mesure de porosit\u00e9 (BET) et la R\u00e9sonance Magn\u00e9tique Nucl\u00e9aires (RMN). Les influences de la longueur du ligand dans l\u2019UiO-67-NH2(Zr) ainsi que la pr\u00e9sence de groupement hydrophile dans l\u2019UiO-67-(NH2)2(Zr) ont \u00e9t\u00e9 \u00e9tudi\u00e9es. Nous mettons en avant une stabilit\u00e9 \u00e0 la vapeur d\u2019eau de certains compos\u00e9s issu de la famille des UiO(Zr) surtout \u00e0 haute temp\u00e9rature (200 \u00b0C) et une destruction partielle \u00e0 basse temp\u00e9rature. De plus, diff\u00e9rents enrichissements en 17O de l\u2019UiO-66(Zr) ont \u00e9t\u00e9 test\u00e9s permettant l\u2019enregistrement de spectres RMN 17O : enrichissement du ligand par m\u00e9canosynth\u00e8se, et\/ou mise en pr\u00e9sence d\u2019eau enrichie. Ces diff\u00e9rentes techniques ont permis de mieux comprendre la r\u00e9activit\u00e9 des diff\u00e9rents sites 17O, et de mettre en avant une certaine labilit\u00e9 des liaisons Zr-O. Enfin des techniques avanc\u00e9es de RMN (basse temp\u00e9rature et s\u00e9quence WURST-QCPMG) ont permis de caract\u00e9riser le cluster de ces compos\u00e9s UiO(Zr) au travers de l\u2019\u00e9tude du noyau de zirconium-91. De l\u00e9g\u00e8res modifications du cluster m\u00e9tallique ont pu \u00eatre pour la premi\u00e8re fois observ\u00e9es quand les compos\u00e9s de la famille des UiO(Zr) sont mis en contact avec de la vapeur d\u2019eau. Enfin, des travaux novateurs sur l\u2019\u00e9laboration sous la forme de films minces de MOF ont \u00e9t\u00e9 initi\u00e9s. Cela doit nous permettre de d\u00e9velopper de nouvelles applications dans le domaine de la micro\u00e9lectronique notamment, en fonctionnalisant le substrat utilis\u00e9.<\/p>\n<h5>Abstract:<\/h5>\n<p>Metal-Organic Frameworks (MOFs) are porous, crystallized hybrid materials consisting of inorganic clusters linked together by organic ligands. The structure of these compounds offers a very important porosity and high specific surfaces (up to several thousands of m\u00b2\/g). However, their use in industrial processes remains poorly developed, mainly due to a lack of knowledge about their reactivity towards water. During this thesis, different techniques were used to study the structural modifications that can occur on UiO-66(Zr) in the presence of water vapor: X-ray diffraction, infrared, porosity measurement (BET) and Nuclear Magnetic Resonance (NMR). The influence of the ligand length in UiO-67-NH2(Zr) as well as the presence of hydrophilic group in UiO-67-(NH2)2(Zr) have been studied. We highlight a stability to water vapor of some compounds from the UiO(Zr) family especially at high temperature (200 \u00b0C) and a partial destruction at low temperature. Moreover, different 17O enrichments of UiO-66(Zr) have been tested allowing the recording of 17O NMR spectra: enrichment of the ligand by mechanosynthesis, and\/or enrichment with water. These different techniques allowed to better understand the reactivity of the different 17O sites, and to highlight a certain lability of the Zr-O bonds. Finally, advanced NMR techniques (low temperature and WURST-QCPMG sequence) allowed to characterize the cluster of these UiO(Zr) compounds through the study of the zirconium-91 core. Slight modifications of the metal cluster could be observed for the first time when the compounds of the UiO(Zr) family are put in contact with water vapor. Finally, innovative work on the elaboration of MOF thin films has been initiated. This should allow us to develop new applications in the field of microelectronics in particular, by functionalizing the substrate used.<\/p>\n<\/div><\/section>","protected":false},"excerpt":{"rendered":"","protected":false},"author":20,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[317],"tags":[],"class_list":["post-55547","post","type-post","status-publish","format-standard","hentry","category-these-2021"],"_links":{"self":[{"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/posts\/55547","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/users\/20"}],"replies":[{"embeddable":true,"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/comments?post=55547"}],"version-history":[{"count":0,"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/posts\/55547\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/media?parent=55547"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/categories?post=55547"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.iemn.fr\/en\/wp-json\/wp\/v2\/tags?post=55547"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}