Metathesis as an alternative synthesis route to layered sulfides A(LiZn)S<sub>2</sub> (A = alkali-metal) with unexpected colors

Stepanjuga, Alexander; Ray, Rajyavardhan; Richter, Manuel; Carrocci, Salvatore; Hampel, Silke; Galle, Lydia; Grafe, H.-J.; Valldor, Martin

doi:10.1039/d1nj05892d

Cited by 1 publication

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References 19 publications

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“…The atom-projected individual DOS contributions at and below the Fermi level ( E F ) are found to be contributed mainly by the O 2p states hybridizing partially with the Cl 3p states, whereas in the conduction region, the Bi 6p state dominates. This shows that the least energy electron transfer is the ligand-to-metal charge transfer from oxygen to bismuth states . A similar trend is noted for the doped cases, except that due to doping, the orbitals shift either toward or away from E F (Figure a–c).…”

Section: Resultssupporting

confidence: 64%

“…This shows that the least energy electron transfer is the ligand-to-metal charge transfer from oxygen to bismuth states. 70 A similar trend is noted for the doped cases, except that due to doping, the orbitals shift either toward or away from E F (Figure 11a The band gap measured between the VBM and CBM gives rise to 2.3 eV. This is the electronic band gap observed between VBM and CBM.…”

Section: •−mentioning

confidence: 99%

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Hole and Electron Doping Outcomes in Bi₂YO₄Cl

Pandey,

Yadav,

Yadav

et al. 2023

Inorg. Chem.

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Recognizing the deficiency in the hole and electron doping outcomes in layered bismuth-based oxyhalides intergrowths, the current study was addressed to the doping of Ca2+ and Zr4+ for Y3+ in Bi2YO4Cl. The samples were rapidly synthesized by a sol–gel auto combustion method and characterized extensively. Up to 30 mol % Y could be substituted with Ca in tetragonal symmetry and without the appearance of any additional phase. The unit cell parameters varied nonlinearly with the elongation of the Y–O bond. The Raman spectra supported the local site distortion. The calcium-substituted samples displayed selected area electron diffraction characteristics similar to those of Bi2YO4Cl. A blueshift of the absorption edge was noticed with increasing calcium content yielding optical band gap values in the 2.40–2.57 eV range. The creation of 10% Bi5+ in Bi2Y0.70Ca0.30O4Cl was established with the help of XPS measurements and redox titrations. The higher reactivity of Bi5+ in an aqueous solution has been demonstrated for the oxidation of As(III) to As(V). Electron doping through Zr4+ incorporation was possible up to 30 mol % in Bi2YO4Cl. The Y–O bonds are contracted, and the Bi–O bonds are elongated with increasing Zr4+ content. Zr4+’s incorporation induced a local distortion. The color of the sample changed from bright yellow to deep yellow with Zr inclusion, resulting in a progressive decrease in optical band gap values. The introduction of electrons caused the reduction of 13.6% of Bi(III) to Bi(0). These results have established the vulnerability of Bi2O2 chains to charge carriers in Bi2YO4Cl. Density functional theory (DFT) calculations were implemented to understand the electronic and optical properties of the pristine and doped compounds. From the band structure calculations, the chosen compounds were found to be indirect band gap semiconductors. The results of the DFT calculations were in good agreement with the experiment; however, for the doped cases, virtual crystal approximation has been used considering uniform doping at the Y-site.

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Section: Resultssupporting

confidence: 64%

Section: •−mentioning

confidence: 99%

Hole and Electron Doping Outcomes in Bi₂YO₄Cl

Pandey,

Yadav,

Yadav

et al. 2023

Inorg. Chem.

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Metathesis as an alternative synthesis route to layered sulfides A(LiZn)S₂ (A = alkali-metal) with unexpected colors

Abstract: Pure powders of Na(LiZn)S2 can be obtained through solid-state reaction, and A(LiZn)S2 (A = K, Rb, Cs) result from metathesis reactions between the alkali-metal chloride and the same constituents used...

Cited by 1 publication

References 19 publications

Hole and Electron Doping Outcomes in Bi₂YO₄Cl

Hole and Electron Doping Outcomes in Bi₂YO₄Cl

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Metathesis as an alternative synthesis route to layered sulfides A(LiZn)S2 (A = alkali-metal) with unexpected colors

Abstract: Pure powders of Na(LiZn)S2 can be obtained through solid-state reaction, and A(LiZn)S2 (A = K, Rb, Cs) result from metathesis reactions between the alkali-metal chloride and the same constituents used...

Cited by 1 publication

References 19 publications

Hole and Electron Doping Outcomes in Bi2YO4Cl

Hole and Electron Doping Outcomes in Bi2YO4Cl

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Metathesis as an alternative synthesis route to layered sulfides A(LiZn)S₂ (A = alkali-metal) with unexpected colors

Hole and Electron Doping Outcomes in Bi₂YO₄Cl

Hole and Electron Doping Outcomes in Bi₂YO₄Cl