Hierarchically?Ordered Materials

Porous materials, in particular microporous zeolites, are the working horses industry mainly as catalysts, adsorbents or ion-exchangers. In order to further improve their performance and open new fields of application, one could take advantage a well on purpose designed hierarchical porous structures overcome, i.e., transport limitation into narrow, interconnected channels with special reactivity selectivity properties. To this themed issue 18 reviews full papers have been contributed from leading research groups field materials zeolites. volume, we collected latest advances respect synthesis, characterization application focus Particular attention is paid development structure-property relationships, which requires use, cutting-edge techniques. The idea was born workshop (HiMat2019) at FAU Erlangen-Nürnberg fall 2019, organized by guest editors. Historically, expression hierarchy goes back Greek words “hieros” (scared) “archein” (rules) describing ranking sanctifications churches due importance. Thus, “hierarchy” had not created systems particular. However, found everywhere; it basic organization principle nature, e.g. trees, leaves, wood, bones, blood circuits, just name few examples. also more general ecological, social, economic, even technical systems. many derive function throughout structural elements. Self-organization processes typically lead these specific structures. Hierarchy always related properties such strength, chemical compositions, properties, like flux, flow profiles etc. porosity natural bones structure circle lounge optimized under aspects strength flux profiles, respectively. performance, properties.[1, 2] introduction zeolite crystals brought out better intrinsic advantages zeolites for certain reactions. adaptation inorganic, material oriented zeolite-based catalysts opens options target design started about 20 years ago initiating area field.[3, 4] Figure 1, number published last 30 years, mentioning key “hierarchical materials” zeolites” compared starting late 90s early 2000s. An exponentially increasing observed 2000 2005, first zeolite-containing were prepared, systems, composites, however, based preformed diatoms and/or glasses silica supports. Depending reaction conditions, both silica-based can act support raw formation. Nevertheless, literature very often used broad sense contain different pore types form bi- multimodal size distributions, independently if how two (or more) interconnected. narrow sense, existence an interplay between levels has be evidenced before overall system “hierarchical”. Accordingly, distinguish (i) (“zeolites” per definition) (ii) either combination zeolitic microspores mesopores (“mesoporous zeolites”, “zeolites mesopores”), macropores (“zeolites macropores” “macroporous zeolites”) combinations thereof (multiple systems). From viewpoint editors, interconnectivity precondition named hierarchical! Materials pores sizes distributions) necessarily hierarchical. Therefore targeted thorough important judgement, classification assessment applicative should show than additive effect additional system. context, topic “Hierarchically-ordered bridges wide range theoretical view preparation strategies methods up (potential) applications. presented topics follows line provide comprehensive unique overview over all junior scientists – students post-docs any other interested member scientific community tutorial contributions. compiles insights synthesis modification selected techniques electron tomography, xenon NMR spectroscopy physical adsorption mercury porosimetry novel aspects. attempt bridge areas, reviewed separately, editors classified evaluated providing containing hierarchically-ordered structures, see article 2001841. authors generalize discuss “toolbox” consisting bottom-up top-down pure composite tailored porosity. establish synthetic efforts combined testing. addition discussion that possess only micropores, Weissenberger co-workers review catalytic macropores, 2001653. They conclude larger some make them attractive adsorptive unselective unspecific sites large surfaces possibility capillary condensation minimized completely suppressed direct micro- macropores. Yu creation titanosilicate TS-1 least porosities aroused growing interest recent its improved overcoming steric diffusional hinderances, 2001095. review, progress construction effective Ti species described. impacts active improvement performances oxidative desulfurization epoxidation reactions highlighted. Current challenges fine adjustment porosities, connectivities, ordering secondary future catalysts. original paper, P?ech report preparation, MFI nanosponge (nsTS-1), 2001288. nsTS-1 prepared post-synthesis titanium impregnation nanosponge, producing fully crystalline highly catalyst high total volume. Due external surface nanolayered domains, isolated framework-attached formed rather extra-framework TiO2. As result, defined uniform layered (e.g., silica– titania pillared TS-1). samples tested cis-cyclooctene, norbornene, linalool using hydrogen peroxide exhibited superior respected conversion classical catalyst. García-Martínez surfactant-templating versatile method introduce intracrystalline mesoporosity 2001388. This proven extremely finely control amount mesopores, while maintaining main features zeolite, crystallinity, acidity, hydrothermal stability. Surfactant-templating successfully applied develop variety including FAU, BEA, MOR, LTL, MFI. textural results excellent industrially relevant processes, ranging fluid cracking pharmaceutical ingredients. result shown surfactant-templated mesoporous Y currently being several refineries. communication Huang proposes simple efficient synthesize ZSM-5 employing water-soluble carbon dots (CDots), 2001846. varied 5 23 nm, allowing Notably, micropore 0.55 small 4.8 7.4 mesopore 17.5 nm 1,3,5-triisopropylbenzene stability parent zeolite. enhanced activity attributed diffusion reactants products possessing size, coking resistance increased accessibility acid sites. paper Valtchev discusses etching aqueous solutions NH4F NH4HF2 alternate pathway generate L, 2000348. Tuning conditions allows without reducing volume L. reported experimental data 1 wt.-% solution etchant able affecting lower amounts fluoride source required concentrated (20–40 wt.-%) solutions. A strategy prepare nanosized faujasite (FAU) sodalite (SOD) topology Mintova co-workers, 2000634. proposed two-step procedure includes formation colloidal suspensions followed separation amorphous precursor nanoparticles, subsequent transformation treatment alkali (NaOH) only. Tiemann Weinberger address selective manipulation ordered 2001153. means when distinct, hierarchical, exist material, each may chosen manipulation. Several achieve goal. Molecules molecule assemblies utilized temporarily protect (soft protection), occurs accessible When distinct functionalization exposed, reactivity/diffusion agent Obviously, species/ reagent plays essential role, access hindered prevented entirely. Selective loading functional e.g., adsorption/separation, energy conversion, catalysis. Reinhard laser-based metallic viz. tin, copper, silicon, titanium, tungsten surfaces, 2000253. impact suitably tuned nanosecond laser pulses triggers process laser-induced metal ablation instantaneous recondensation partially oxidized metals cauliflower-like superstructures comprising hybrid micro-/nanopatterning. Repeated scanning intense focused beam creates microstructures hierarchically tunable layer-by-layer design. introduced concept enables convenient environmentally technologically areas storage, sensing Five contributions devoted depth hierarchically-organized prerequisite understanding relationships. Apeleo Zubiri explore capabilities correlative 360° tomography (ET) lab-based nano X-ray computed (Nano-CT) enabling 3D analyses volumes (60 µm)³ down resolution.[5] demonstrated particles embedded By applying same particle higher resolution fidelity ET segmentation space Nano-CT reconstruction. Extended statistical relevance interparticle obtained reconstructions agglomerates, large-field-of-view mode Nano-CT. approach real characteristics comparison complementary Moreover, investigating stages 360°-ET mechanism materials. Investigations still stage beginning. Hwang mass transfer various parameters, notably diffusivities spaces, relative populations exchange rates, 2000749. Their quantified two-region model (Kärger equations). underlying formalism offer tool assessing description transfer, parallel specification limiting cases reflection measurements crucial optimal enhancement technological exploitation Wisser Hartmann 129Xe adsorbed most powerful probe sizes, geometry 2001266. Adsorbed walls, acts nucleus. (tutorial) principles models developed determine given. possibilities limitations obtaining highlighted works presented. Schlumberger Thommes 2002181. lies advanced physisorption methodologies micro-mesopore analysis, but addresses macroporosity porosimetry. Fundamental concepts major mechanisms associated phase behavior fluids discussed much detail. conjunction case studies, determination reliable volumes, distributions information network characteristics. Rather serving literature, offers guidance nanoporous intrusion/extrusion. Coppens multiscale modelling approaches optimize 2001409. It provides methodology rules thumb guide Inspiration taken leaves tissues, similar requirements features. hierarchically-structured added macro-/mesopore fraction, connectivity, crystal minimum crucial, distribution secondary. No uncontrolled within crystals. Surface barriers, significantly affect, dominate transport. Understanding origin ways emergent area. catalysis benefit computer-assisted network, embracing networks scalable efficiency, robustness. group will opportunities hierarchically-designed sensing, change photocatalysis. Enke, Tallarek investigated influence sol–gel component acetylcholinesterase enzyme array response time, 2000163. meso-macroporous monomodal (of macropores) regarding functionality efficiency reflected apparent rates. manifested maximum purely macroporous material. presence hand turn reduces time. Ogura propose CHA carrier docosane (C22) use (PCM), 2001085. Owing physicochemical PCM-containing adsorbent dual functions, namely simultaneous adsorption, heat storage. chabazite-type SSZ-13 loaded via vapor PCMs located inside micropores dehumidification process. afforded bed temperature ramping, owing recovery generated upon H2O through PCM. Su ternary three-dimensional (3DOM) heterojuncted nanocomposites (3DOM-Pt/Bi2MoO6/TiO2) multifunctional platform photocatalytic dye degradation, photoelectrocatalytic (PEC) water splitting thermal-catalytic toluene decomposition, 2001879. remarkably degradation PEC activities effects light harvesting, abundant reactive sites, facile charges-holes pair separation. Catalysts Pt Bi2MoO6, exhibit highest rhodamine B rate activity, 10 3.4 times, respectively, reference photonic (PC-TiO2) photocatalyst. work clearly illustrated photocatalyst 3DOM intimate heterostructure facilitate intermediates photogenerated carriers. applications photocatalysis photoelectrochemistry. We hope you find beneficial your teaching endeavors. Finally, would thank Wiley editorial staff Anna Troeger invaluable acknowledge generous funding Bayerisch-Tschechische Hochschulagentur (BTHA) grant agreement FV-17, supported our HiMat2019. Martin his Ph.D. Physical Chemistry 1993. He held postdoctoral positions University Houston (1994-1995), Stuttgart (1996-1999) finished habilitation Chemical Technology TU Kaiserslautern 2002. he became Professor Advanced Science Augsburg. joined Friedrich-Alexander-Universität 2009 Catalysis Director Erlangen Center Interface Research (ECRC). His interests spectroscopic catalysis, Currently, serves president International Zeolite Association (IZA). Wilhelm Schwieger academic grades Martin-Luther-University Halle-Wittenberg (MLU). After receiving 1979, hold position industry, where responsible production. 1989 overtook assistant professorship Institute Technical (MLU), running ‘Crystalline Silicates’ Before taking final appointment 1998, carry stays universities Vancouver, Karlsruhe Prague. Since April 2019 pensioned. Matthias Ph.D 1993 TU-Berlin. 1992–1995 Project Scientist EURECA mission European Space Agency (ESA). 1996, moved ESA fellow/Research Associate Maryland, College Park, USA. Quantachrome Corp. 2001–2018 Scientific (Boynton Beach, FL, USA). 2018 Head Separation Erlangen-Nürnberg. holds Visiting Edinburgh (since 2012), U.K Lorraine University, Nancy, France 2017).