Identification of Barium Hydroxo-Hydroperoxostannate Precursor for Low-Temperature Formation of Perovskite Barium Stannate

Medvedev, Alexander G.; Mikhaylov, Alexey A.; Shames, Alexander I.; Churakov, Andrei V.; Grishanov, Dmitry A.; Melnik, E. A.; Tripol’skaya, T. A.; Lev, Ovadia; Prikhodchenko, Petr V.

doi:10.1021/acs.inorgchem.0c02993

Cited by 13 publications

(8 citation statements)

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“…Adding an excess of 98 wt % H 2 O 2 obtained from serine perhydrate ([H 2 O 2 ]/[Pb] = 5:1) leads to a complete disappearance of this peak and the emergence of a broad resonance at δ −139.6 (Figure b), which reflects the replacement of the hydroxo by the hydroperoxo group in the coordination environment of lead(IV) atoms. A similar high-field shift was previously reported for hydroperoxo/hydroxo substitution in the coordination environment of Sn(IV). , The observed line broadening of the signal at −139.6 is attributed to the chemical exchange owing to reversible oligomerization of the triphenyl hydroperoxo lead(IV) complex, which is also typical for other p-block elements in hydrogen peroxide-containing systems, as previously demonstrated for boron, germanium, , tin(IV), ,, and tellurium(VI) complexes . Oligomeric (Ph 3 Pbμ-OOH) n species can be considered as intermediates leading to the crystallization of the one-dimensional (1D) coordination polymer 1 .…”

Section: Resultssupporting

confidence: 82%

“…A similar highfield shift was previously reported for hydroperoxo/hydroxo substitution in the coordination environment of Sn(IV). 46,47 The observed line broadening of the signal at −139.6 is attributed to the chemical exchange owing to reversible oligomerization of the triphenyl hydroperoxo lead(IV) complex, which is also typical for other p-block elements in hydrogen peroxide-containing systems, as previously demonstrated for boron, 48 germanium, 49,50 tin(IV), 46,47,51 and tellurium(VI) complexes. 52 Oligomeric (Ph 3 Pbμ-OOH) n species can be considered as intermediates leading to the crystallization of the one-dimensional (1D) coordination polymer 1.…”

Section: ■ Results and Discussionsupporting

confidence: 68%

“…The confusion of superoxo with hydroperoxo functionality is not unusual. For example, a crystalline superoxide molecular cluster was proposed as a low-temperature precursor for a highly efficient barium stannate perovskite solar cell, but this was later identified as a superoxide–free barium trihydroxo(hydroperoxo)peroxo stannate, BaSn(OH) 3 (OOH)(OO) phase . Interestingly, the latter belongs to the coordination polymers, and its crystal structure can be described as a 3D coordination peroxo polymer.…”

Section: Resultsmentioning

confidence: 99%

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Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis

et al. 2022

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The synthesis, transformation, and application in catalysis of triphenyllead hydroperoxide, the first dioxygen lead complex, are described. Triphenyllead hydroperoxide is characterized by 207Pb nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and single-crystal X-ray diffraction, revealing the first one-dimensional (1D) coordination peroxo polymer. Photolytic isomorphous transformation of Ph3PbOOH yields a mixed hydroxo/superoxo crystalline structure, the first nonalkali superoxo crystalline metal salt, which is stable up to 100 °C. Upon further photolysis, another isomorphous transformation of the superoxide to hydroxide is observed. These are the first single-crystal-to-single-crystal hydroperoxide-to-superoxide and then to hydroxide transformations reported to date. Photolysis of triphenyllead hydroperoxide yields two forms of superoxide-doped crystalline structures that are distinguished by widely different characteristic relaxation times. The use of Ph3PbOOH as an easy-to-handle solid two-electron oxidant for the highly enantioselective epoxidation of olefins is described.

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Section: Resultssupporting

confidence: 82%

Section: ■ Results and Discussionsupporting

confidence: 68%

Section: Resultsmentioning

confidence: 99%

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Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis

et al. 2022

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“…33 BaSn-related nanoscale materials show promising appli-34 cation in the sewage treatment field owing to their good 35 electronic and photocatalytic properties [1−3]. Perovskite-36 structured Ba stannate hexahydroxy with the formula 37 BaSn(OH) 6 consists of corner shared Sn(OH) 6 polyhedra 38 and shows good semiconductor photocatalytic performance 39 [4,5]. Tin oxide (SnO 2 ) belongs to an n-type semiconductor 40 with a direct band-gap energy of 3.6 eV, demonstrating ex-41 cellent photocatalytic and sensing properties [6−8].…”

Section: Introductionmentioning

confidence: 99%

Enhancing the Photocatalytic Performance of BaSn-based Composites by Doping Rare Metals

Sun

Wang

Tao

et al. 2022

e-J. Surf. Sci. Nanotechnol.

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Rare metal (La or Nd) doped BaSn-based composites with highly polycrystalline nature were successfully synthesized through a simple hydrothermal route.The doped composites were investigated by X-ray diffraction, electron microscopy, solid ultraviolet diffuse reflectance spectrum, X-ray photoelectron spectroscopy, photoluminescence, electrochemical impedance spectroscopy, and photocatalytic measurements. La and Nd doping induces the morphological change of the BaSn-based composites from the nanorods to irregular nanoscale particles with the average size of about 100 nm. La and Nd in the doped composites exist in the form of cubic La 2 Sn 2 O 7 and cubic Nd 2 Sn 2 O 7 phases. The absorption edge of the doped composites red-shifts comparing with that of the non-doped composites. The doped BaSn-based composites with the La or Nd mass ratio of 8 wt% possess the smallest band-gap energy in the doped composites and the good light absorption ability. The La or Nd doping mass ratio has an important role in the photocatalytic degradation of the crystal violet (CV) dye. The CV molecules in the 20-mL CV solution with 10 mg L −1 can be totally removed by the 20-mg La-or Nd-doped BaSn-based composites under the light irradiation for 150 min. Scavenger experiments show that hydroxyl free radicals (•OH) and superoxide anion radicals (•O 2 − ) are effective oxidizing agents for CV degradation. Photoluminescence and electrochemical impedance spectroscopy show that the significant decrease in the recombination ability of the electron and hole pairs by the rare metal doping is of great importance for enhancing the photocatalytic activity of the BaSn-based composites. The La-or Nd-doped BaSn-based composites show good reusability for CV degradation. Keywords BaSn-based composites; Rare metal; Doping; Crystal violet; Photocatalysis 42 et al. [9] reported that the tin oxide nanospheres had large 43 specific surface area with the value of about 160 m 2 g −1 and 44 exhibited good photocatalytic activity towards methyl or-45 ange (MO) under the ultraviolet (UV) light with good pho-46 tocatalytic recyclability. Very recently, BaSn-based nanorods 47 with monoclinic BaSn(OH) 6 and orthorhombic SnO 2 phases, 48 50−150 nm in diameter, were successfully prepared by our 49 group [10]. The obtained BaSn-based nanorods possessed a 50 band-gap energy of 3.74 eV and showed good photocatalytic 51 activity towards crystal violet (CV) under the UV light irra-52 diation. However, the band-gap energy of the BaSn-based 53 nanorods is large and is restrictive for the application in the 54 photocatalytic field. Therefore, it is essential to develop ef-55 ficient method to decrease the band-gap energy and to en-56 hance the photocatalytic properties of the BaSn-based na-firstly investigated by analyzing the relationship between the 359 CV concentration change ratio (C/C 0 ) and the UV light irra-360 diation time. The CV degradation efficiency was calculated 361 according to the following equation: CV degradation effi-362 ciency % = (1 − C/C 0 ) × 100, where ...

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“…37 and Medvedev et. al., 38 conducted a detailed study on this method to address the reproducibility issues and correctly identify the precursor, respectively. The various moieties present as ligands in the CSMC precursor are identied as a combination of hydroxo, hydroperoxo, peroxo, and superoxo species.…”

Section: Introductionmentioning

confidence: 99%

Alcohol Assisted Solution-Combustion Technique for the Synthesis of Phase-Pure BaSnO3 Nanoparticles at 130 °C

Chawla

Aggarwal

Kumar

et al. 2021

Preprint

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Lowering the synthesis temperature to obtain phase pure BaSnO3, which is the host material for high figure-of-merit (FOM) perovskite transparent conductors (TCs), can expand the horizons for its optoelectronic applications, with an obvious reduction in the thermal budget. In this work, we have developed a novel solution combustion technique for the synthesis of BaSnO3 nanoparticles. A peroxo/superoxo precursor to the nanoparticles is first synthesized by co-precipitation of the tin and barium salts via the H2O2 assisted or the `CSMC' route. The phase evolution, under different drying conditions of the wet precursor to crystalline BaSnO3 nanoparticles is then studied. We find that the crystallization temperature of BaSnO3 is significantly reduced by adding an organic solvent such as ethanol or propanol to the precursor; temperatures as low as 130 °C yield phase pure BaSnO3 nanoparticles. We establish that the organic solvent increases the reactive O2 ligand content, which plays a pivotal role in the synthesis. Due to this, an exothermic reaction occurs around 130 °C, thereby providing the heat of reaction for conversion of the precursor to phase-pure BaSnO3. Importantly, this method should also allow for the facile incorporation of dopants, paving the way for synthesis of high FOM TCs at low temperatures. Such low synthesis temperatures enable BaSnO3 to be used in devices having temperature limitations during device processing, such as heterojunction Si solar cells or perovskite-based solar cells in an n-i-p architecture.

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Identification of Barium Hydroxo-Hydroperoxostannate Precursor for Low-Temperature Formation of Perovskite Barium Stannate

Cited by 13 publications

References 39 publications

Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis

Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis

Enhancing the Photocatalytic Performance of BaSn-based Composites by Doping Rare Metals

Alcohol Assisted Solution-Combustion Technique for the Synthesis of Phase-Pure BaSnO3 Nanoparticles at 130 °C

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