Cerium-oxo clusters for photocatalytic aerobic oxygenation of sulfides to sulfoxides

Lv, Xing; Zhao, Xiao‐Li; Zhao, Qixin; Zheng, Qi; Xuan, Weimin

doi:10.1039/d2dt00856d

Cited by 6 publications

(6 citation statements)

References 56 publications

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“…As shown in Scheme 2, under white LED light irradiation, LCU-20 could be excited and electron transfer occurred. Simultaneously, MPS lost electrons to form the corresponding radical cation (MPS radical cation) through photogenerated holes in the HOMO orbitals of LCU-20 , 48 and O 2 was reduced to the reactive oxygen species O 2 ˙ − by photogenerated electrons in the LUMO orbitals. 49 Subsequently, O 2 ˙ − combined with the radical cation to further form the methyl phenyl persulfoxide intermediate.…”

Section: Resultsmentioning

confidence: 99%

The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

Huang

Liu

Zhou

et al. 2023

Inorg. Chem. Front.

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Section: Resultsmentioning

confidence: 99%

The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

Huang

Liu

Zhou

et al. 2023

Inorg. Chem. Front.

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“…State-of-the-art preparation of monodisperse ceria nanoparticles are often executed in organic solvent with capping groups to control and maintain particle size. ,− Additionally, molecular Ce IV clusters have been crystallized from all types of media and with different capping groups, − highlighting the tendency of Ce IV to undergo hydrolysis/condensation reactions. Of these, a subfamily of spherical clusters consisting of 16, 19, 24, 38, 40, and 100 Ce-polyhedra have been crystallized from organic media with carboxylate and solvent capping ligands, − and Ce 38 has also been isolated from HCl solution . In this family, the arrangement of the Ce-polyhedra resembles that of CeO 2 , and their sizes (specifically Ce 38 , Ce 40 , and Ce 100 ) are similar to the observed primary particle size of CeO 2 that precipitates from aqueous cerium ammonium nitrate (CAN) .…”

Section: Introductionmentioning

confidence: 99%

Cerium Nanophases from Cerium Ammonium Nitrate

Palys,

Stephen,

Mao

et al. 2024

Langmuir

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Ceria nanomaterials with facile Ce III/IV redox behavior are used in sensing, catalytic, and therapeutic applications, where inclusion of Ce III has been correlated with reactivity. Understanding assembly pathways of CeO 2 nanoparticles (NC-CeO 2 ) in water has been challenged by "blind" synthesis, including rapid assembly/precipitation promoted by heat or strong base. Here, we identify a layered phase denoted Ce−I with a proposed formula Ce IV (OH) 3 (NO 3 )•xH 2 O (x ≈ 2.5), obtained by adding electrolytes to aqueous cerium ammonium nitrate (CAN) to force precipitation. Ce−I represents intermediate hydrolysis species between dissolved CAN and NC-CeO 2 , where CAN is a commonly used Ce IV compound that exhibits unusual aqueous and organic solubility. Ce−I features Ce−(OH) 2 −Ce units, representing the first step of hydrolysis toward NC-CeO 2 formation, challenging prior assertions about Ce IV hydrolysis. Structure/composition of poorly crystalline Ce−I was corroborated by a pair distribution function, Ce-L3 XAS (X-ray absorption spectroscopy), compositional analysis, and 17 O nuclear magnetic resonance spectroscopy. Formation of Ce−I and its transformation to NC-CeO 2 is documented in solution by small-angle X-ray scattering (SAXS) and in the solid-state by transmission electron microscopy (TEM) and powder X-ray diffraction. Morphologies identified by TEM support form factor models for SAXS analysis, evidencing the incipient assembly of Ce−I. Finally, two morphologies of NC-CeO 2 are identified. Sequentially, spherical NC-CeO 2 particles coexist with Ce−I, and asymmetric NC-CeO 2 with up to 35% Ce III forms at the expense of Ce−I, suggesting direct replacement.

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“…One of the most notable industrial applications of ceria is its use in three-way catalysts (TWCs); ceria can serve several purposes for TWCs, including acting as an oxygen storage component due to its reduction potential. , In fact, the accessibility of the +3 and +4 oxidation states prompts many efforts that seek to harness the redox chemistry of cerium toward uses in optics, solid-oxide fuels, and oxygen storage. − Largely motivated to (1) better understand the catalytic behavior of CeO 2 and (2) develop novel Ce-based catalysts that can be fine-tuned for specific applications, the chemistry community has become interested in cerium-oxo clusters. These species can be regarded as molecular scale nanoparticles of CeO 2 , and their properties seem to depend on the nuclearity and composition of the Ce cluster . As a testament, Christou et al recently demonstrated the ability of Ce-oxo clusters to scavenge reactive oxygen species, and the activity of these clusters was dependent on the number of Ce III atoms present in the cluster .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate

Blanes-Díaz,

Shohel,

Rice

et al. 2023

Inorg. Chem.

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Cerium-oxo clusters have applications in fields ranging from catalysis to electronics and also hold the potential to inform on aspects of actinide chemistry. Toward this end, a ceriumacetylacetonate (acac 1− ) monomeric molecule, Ce(acac) 4 (Ce-1), a n d t w o a c a c 1 − -d e c o r a t e d c e r i u m -o x o c l u s t e r s , [Ce 10 O 8 (acac) 14 (CH 3 O) 6 (CH 3 OH) 2 ]•10.5MeOH (Ce-10) and [Ce 12 O 12 (OH) 4 (acac) 16 (CH 3 COO) 2 ]•6(CH 3 CN) (Ce-12), were prepared and structurally characterized. The Ce(acac) 4 monomer contains Ce IV . Crystallographic data and bond valence summation values for the Ce-10 and Ce-12 clusters are consistent with both clusters having a mixture of Ce III and Ce IV cations. Ce L 3 -edge X-ray absorption spectroscopy, performed on Ce-10, showed contributions from both Ce III and Ce IV . The Ce-10 cluster is built from a hexameric cluster, with six Ce IV sites, that is capped by two dimeric Ce III units. By comparison, Ce-12, which formed upon dissolution of Ce-10 in acetonitrile, consists of a central decamer built from edge sharing Ce IV hexameric units, and two monomeric Ce III sites that are bound on the outer corners of the inner Ce 10 core. Electrospray ionization mass spectrometry data for solutions prepared by dissolving Ce-10 in acetonitrile showed that the major ions could be attributed to Ce 10 clusters that differed primarily in the number of acac 1− , OH 1− , MeO 1− , and O 2− ligands. Small angle X-ray scattering measurements for Ce-10 dissolved in acetonitrile showed structural units slightly larger than either Ce 10 or Ce 12 in solution, likely due to aggregation. Taken together, these results suggest that the acetylacetonate supported clusters can support diverse solution-phase speciation in organic solutions that could lead to stabilization of higher order cerium containing clusters, such as cluster sizes that are greater than the Ce 10 and Ce 12 reported herein.

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Cerium-oxo clusters for photocatalytic aerobic oxygenation of sulfides to sulfoxides

Abstract: Two cerium-oxo clusters (COCs) 1 and 2 are constructed by self-assembly of cerium ions and carboxylate ligands. Both clusters feature spherical structures resembling the key moiety of fluorite phase CeO2,...

Cited by 6 publications

References 56 publications

The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

The tail of imidazole regulated the assembly of two robust sandwich-type polyoxotungstate-based open frameworks with efficient visible-white-light-driven catalytic oxidation of sulfides

Cerium Nanophases from Cerium Ammonium Nitrate

Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate

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