The identification and quantification of defects are undoubtedly thorough challenges in the characterization "defect-engineered" metal–organic frameworks (MOFs). UiO-66, known for its exceptional stability defect tolerance, has been a popular target defect-engineering studies. Herein, we show that synthesizing UiO-66 presence an excess benzoic acid is reliable method obtaining samples with very high concentration missing-cluster defects, allowing one to modulate specific properties (i.e.,...

The development of an efficient photocatalyst for C2 product formation from CO2 is urgent importance toward the deployment solar-fuel production. Here, we report a template-free, cost-effective synthetic strategy to develop carbazole-derived porous organic polymer (POP)-based composite catalyst. catalyst comprised In2.77S4 and (POP) held together by induced-polarity-driven electrostatic interaction. Utilizing synergy catalytically active In centers light-harvesting POPs, showed 98.9%...

The introduction of Ce4+ as a structural cation has been shown to be promising route redox active metal-organic frameworks (MOFs). However, the mechanism by which these MOFs act catalysts remains unclear. Herein, we present detailed study site in [Ce6 O4 (OH)4 ]-based such Ce-UiO-66, involved aerobic oxidation benzyl alcohol, chosen model reaction. X-ray absorption spectroscopy (XAS) data confirm reduction up one ion per Ce6 cluster with corresponding outwards radial shift due larger radius...

We report a synthetic strategy to link titanium-oxo (Ti-oxo) clusters into metal-organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF was synthesized by evaporation solution containing Ti-oxo Ti

Tailoring the characteristics of gating transitions in porous network, Ni₂(ndc)₂dabco, was achieved by systematically adjusting critical synthesis parameters.

Bimetallic Ce/Zr-UiO-66 metal-organic frameworks (MOFs) proved to be promising materials for various catalytic redox applications, representing, together with other bimetallic MOFs, a new generation of porous structures. However, no direct proof the presence both metals in single cornerstone UiO-type MOFs was reported so far. Employing element-selective X-ray absorption spectroscopy techniques herein, we demonstrate, first time, that our synthesis route allows obtaining desired Ce content...

A zirconium metal–organic framework with UiO-66 topology was synthesized using a 1,4-naphthalenedicarboxylic acid (NDC) linker (UiO-66-NDC). From synchrotron powder X-ray diffraction (PXRD), we found that the naphthalene rings of NDC are out (a,c)-plane equilibrium by 30°, similar to situation single crystal XRD for benzene in UiO-67 (Cryst. Growth Des. 2014, 14, 5370). Different fractions benzene-carboxylic (BC) modulator versus were used tune structural properties final product. The...

The peculiar mechanism of cooperative CO 2 adsorption in a perfluorinated Ce IV -based metal–organic framework with MIL-140 topology is disclosed using combination experimental and computational methods.

Surface plasmon resonance peak probed by operando UV-vis diffuse reflectance spectroscopy allows for the monitoring of metal nanoparticles formation on an Au/α-Al 2 O 3 catalyst and evaluation their size stability in reaction conditions.

Cu-exchanged chabazite zeolites (Cu-CHA) are effective catalysts for the NH3-assisted selective catalytic reduction of NO (NH3-SCR) abatement NOx emission from diesel vehicles. However, presence a small amount SO2 in exhaust gases leads to severe low-temperature activity these catalysts. To shed light on nature such deactivation, we characterized Cu-CHA catalyst under well-defined exposures using situ X-ray absorption spectroscopy. By varying pretreatment procedure prior exposure, have...

Abstract The two Ce IV MOFs [Ce 6 O 4 (OH) ( TzTz ) ] Ce_TzTz and PyPy 2 Ce_TzTz_PyPy ; H = [2,2′‐bithiazole]‐5,5′‐dicarboxylic acid, 2,2′‐bipyridine‐5,5′‐dicarboxylic acid) are prepared starting from a pre‐formed glycinate‐capped cluster. N isotherms collected at 77 K revealed BET specific surface areas of 1136 238 m g −1 , respectively. Their CO adsorption capacity is assessed T 273 298 p 1 bar. shows the highest gas uptake (7.9 9.7 wt% 11.5 12.5 for O, respectively). More interestingly,...

The use of the V-shaped linker molecules 4,4'-oxydibenzoic acid (H2ODB) and 4,4'-carbonyldibenzoic (H2CDB) led to discovery two isoreticular Ce(IV)-based metal-organic frameworks (MOFs) composition [CeO(H2O)(L)], L = ODB2-, CDB2-, denoted CAU-58 (CAU Christian-Albrechts-University). recently developed Ce-MOF synthesis approach in acetonitrile as solvent proved effective accessing Ce(IV)-MOF structures with infinite rod-shaped inorganic building units (IBUs) circumventing formation...

Cu-exchanged zeolites are widely studied materials because of their importance in industrial energetic and environmental processes. Cu redox speciation lies at the center many these processes but is experimentally difficult to investigate a quantitative manner with regular laboratory equipment. This work presents novel technique for this purpose that exploits selective adsorption CO over accessible Cu(I) sites quantify them. In particular, isothermal volumetric measurements performed 50 °C...

<italic>In situ</italic> FTIR and DFT modelling were used to study the stoichiometry of hexanuclear clusters in Ce/Zr-UiO-66 compounds.

Metal-organic frameworks (MOFs) and covalent organic (COFs) are two innovative classes of porous coordination polymers. MOFs three-dimensional materials made up secondary building blocks comprised metal ions/clusters ligands whereas COFs 2D or 3D highly solids by light elements (i.e., H, B, C, N, O). Both COFs, being conjugated scaffolds, very promising as photoactive for applications in photocatalysis artificial photosynthesis because their tunable electronic properties, high surface area,...

Abstract We report a synthetic strategy to link titanium‐oxo (Ti‐oxo) clusters into metal‐organic framework (MOF) glasses with high porosity though the carboxylate linkage. A new series of MOF was synthesized by evaporation solution containing Ti‐oxo Ti 16 O (OEt) 32 , linkers, and m ‐cresol. The formation linkages between linkers confirmed Fourier‐transform infrared (FT‐IR) spectroscopy. structural integrity within evidenced both X‐ray absorption near edge structure (XANES) 17 magic‐angle...

The new Ce(III) based metal–organic framework Ce2(NDC)3(DMF)2, containing the simple ditopic linker napthalenedicarboxylate (NDC2–), has been synthesized under solvothermal reaction conditions with high purity and yield. Its crystal structure was determined single-crystal X-ray diffraction (SC-XRD) techniques further confirmed by Ce K-edge absorption spectroscopy (XAS). Upon thermal activation compound revealed a phase transformation at about 300 °C involving removal of solvent molecules,...

The key role of K+ counterions in determining the high CO2 capacity UTSA-16 has been highlighted thanks to a combined use situ infrared and 13C solid-state NMR spectroscopies performed controlled atmosphere at variable temperature pressure. A second family sites, engaged higher or coverage, was identified organic linker. Variable IR measurements molecular hydrogen 15 K allowed further distinguish sites two families, slightly different their polarizing ability indistinguishable on basis...

In this article we report on the spectroscopic and adsorptive studies done Ce(III)-based MOF possessing, upon desolvation, open metal sites, a discrete surface area. The Ce-based was synthesized from terephthalic acid linker (H2BDC) Ce3+ cations by classical solvothermal method. Preliminary powder X-ray diffraction analysis showed that obtained materials corresponded to ones reported other authors. Spectroscopic techniques, such as XAS in situ FTIR with probe molecules were used....

Platinum is commonly applied as the anode material for Kolbe electrolysis of carboxylic acids thanks to its superior performance. Literature claims that formation a barrier layer on Pt in acid electrolyte suppresses competing oxygen evolution and promotes anodic decarboxylation. In this work, we show by using combination complementary in-situ ex-situ surface sensitive techniques, presence acetate ions also prevents passive oxide platinum at high potentials. Furthermore, dissolves actively...

The thermolabile acetylene dicarboxylic acid has been introduced as linker in UiO-66 topology, synthetizing the compound with formula [Ce6O4(OH)4(ADC)6] and denoted Ce-UiO-66-ADC MOF. characterization by multi-technique approach coupled computational modelling revealed a peculiar intrinsic defective nature related to of linker.

Scale-up of an Fe-MOF and elucidation its water adsorption properties by PXRD, sorption measurements molecular simulations are reported.

Hard X-ray absorption spectroscopy (XAS) is frequently applied in catalysis and gas sorption studies to monitor changes oxidation states, coordination numbers, interatomic distances of active sites under situ operando conditions. However, transmission XAS data can reveal also the change total amount guest species adsorbed on whole sample. Surprisingly, best our knowledge, latter property has never been exploited. Here, we present a simple method quantify adsorbates from collected during...