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 glasses was synthesized by evaporation of solution containing Ti-oxo clusters Ti O (OEt) , linkers, and m-cresol. The formation of carboxylate linkages between the Ti-oxo clusters and the carboxylate linkers was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The structural integrity of the Ti-oxo clusters within the glasses was evidenced by both X-ray absorption near edge structure (XANES) and O magic-angle spinning (MAS) NMR. After ligand exchange and activation, the fumarate-linked MOF glass, termed Ti-Fum, showed a N Brunauer-Emmett-Teller (BET) surface areas of 923 m g , nearly three times as high as the phenolate-linked MOF glass with the highest BET surface area prior to this report.
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http://dx.doi.org/10.1002/anie.202300003 | DOI Listing |
J Am Chem Soc
December 2024
Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul 08826, Republic of Korea.
Enzymes, composed of earth-abundant elements, outperform conventional heterogeneous photocatalysts in hydrogen production due to the dual-site cooperation between adjacent active metal sites and proton-transferring ligands. However, the realization of such dual-site cooperation in heterogeneous catalytic systems is hindered by the challenges in the precise construction of cooperative active sites. In this study, we present the design of a structurally tuned metal-organic framework (MOF) photocatalyst that incorporates cooperative Brønsted acid-single atom catalytic sites.
View Article and Find Full Text PDFJ Colloid Interface Sci
February 2025
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, China.
The core-shell structure often exhibits unique properties, resulting in superior physical and chemical performance distinct from individual component in the field of photocatalysis. However, traditional prepared methods such as template synthesis and layer-by-layer self-assembly are relatively complex. Therefore, it is necessary to explore an efficient and expedient approach.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry and Biochemistry, The University of Oklahoma, Norman, Oklahoma 73019, United States.
Titanium dioxide (TiO) has long been employed as a (photo)electrode for reactions relevant to energy storage and renewable energy synthesis. Proton-coupled electron transfer (PCET) reactions with equimolar amounts of protons and electrons at the TiO surface or within the bulk structure lie at the center of these reactions. Because a proton and an electron are thermochemically equivalent to an H atom, these reactions are essentially H atom transfer reactions.
View Article and Find Full Text PDFNanoscale
September 2024
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Through modulating the multidentate ligands, solvent environments, and inorganic tin precursors during the synthesis processes, we have successfully prepared a series of unprecedented heterometallic Sn-Ti oxo clusters with structural diversity and different physiochemical attributes. Initially, two Sn6Ti10 clusters were synthesized using trimethylolpropane as a structure-oriented ligand and SnCl·5HO as a tin source. Then, when a larger pentadentate ligand di(trimethylolpropane) was used instead of trimethylolpropane and aprotic acetonitrile solvent was introduced into the reaction system, four low-nuclearity Sn-Ti oxo clusters were discovered, including two Sn1Ti1, one Sn2Ti2 and one Sn2Ti6.
View Article and Find Full Text PDFDalton Trans
August 2024
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan.
Although molecular tetrahedral Ti-oxo species exhibit unique electronic and photochemical properties due to their discrete energy levels, which are different from those of anatase and rutile, such Ti-oxo species are generally unstable and readily transformed to amorphous/crystalline TiO (bulk phases, nanoparticles and clusters) hydrolysis and condensation. Here, molecular Ti-oxo species were immobilised within mesoporous silica SBA-15 by grafting titanium(IV) oxyacetylacetonate using the surface silanol groups of SBA-15 as a scaffold, followed by chemical etching with dilute hydrochloric acid to form molecular TiO species. These Ti species mainly exist as isolated tetrahedrally coordinated structures, as was confirmed by diffuse reflectance UV-vis and Raman spectroscopy.
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