Synthesis and characterization of a new series of BiOI1−x−yBrxCly pigments

doi:10.1016/0022-3697(85)90174-X

Journal of Physics and Chemistry of Solids

Volume 46, Issue 3, 1985, Pages 325-330

https://doi.org/10.1016/0022-3697(85)90174-X Get rights and content

Abstract

New bismuth oxyhalides of the type BiOI_1−xBr_x, form a complete solid solution series and crystallize in a layered tetragonal matlockite structure Color varies from yellow to red as x decreases from 0 75 to 0 and layer separation, c, increases from 8 45 to 9 16 Å The compounds have large intrinsic optical absorption coefficients (α > 10⁵ cm^-1). Used as pigments, they are light-fast but show less color saturation than PbCrO₄ of the same hue.

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Cited by (28)

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Layered oxyiodides with a Sillén-Aurivillius structure ([Bi₂O₂][A_n₋₁B_nO₃_n₊₁][Bi₂O₂][X]; X = halide, n = number of perovskite layers) have attracted much attention as promising photocatalysts for visible-light-induced water splitting. Changing the number of perovskite layers in oxychlorides provides broad structural variations. However, there are no reports on the synthesis of Sillén-Aurivillius oxyiodides with n ≥ 3 due to unestablished synthetic methods. Three novel oxyiodides, namely, BaBi₅Ti₃O₁₄I (n = 3), Ba₂Bi₅Ti₄O₁₇I (n = 4), and Ba₃Bi₅Ti₅O₂₀I (n = 5) with triple-, quadruple-, and quintuple-perovskite layers, respectively, were synthesized in this study by investigating and optimizing the synthetic routes in the solid-state reaction. The results reveal that the key to achieving the single-phase synthesis of multi-layered oxyiodides is avoiding the use of low-reactivity Aurivillius compounds as raw materials. The obtained oxyiodides possessed narrower band gaps than their chloride and bromide counterparts, as well as appropriate band levels for water splitting. They functioned as photocatalysts for water (reduction) and oxidation under (UV-) visible light; notably BaBi₅Ti₃O₁₄I exhibited significantly higher photocatalytic O₂ evolution than the other oxyiodides and chloride/bromide counterparts.
Dual modification of BiOIO<inf>3</inf> via doping iodine and fabricating heterojunction with basic bismuth salt: Facile synthesis, superior performance for degradation of multiple refractory organics
2022, Journal of Environmental Chemical Engineering
Citation Excerpt :
A two-step process was utilized to realize the double modification of BiOIO3, i.e. iodine doping and construction of heterojunction with [Bi6O6(OH)3](NO3)3∙1.5H2O (BHN). In a typical process, the BiOI powders were firstly prepared by a facile chemical bath method at room temperature based on the procedure described in the literature [26]. Then, 3.6373 g Bi(NO3)3∙5H2O was dissolved in 40 mL of nitric acid aqueous solution (4 M).
An approach of simultaneous iodine doping and heterojunction fabricating with basic bismuth salt was proposed, Based on this, a novel I/BiOIO₃/[Bi₆O₆(OH)₃](NO₃)₃∙1.5H₂O (I/BiOIO₃/BHN) photocatalyst was prepared. The photocatalytic activity was evaluated by the degradation of multiple refractory pollutants (rhodamine B, methyl orange, phenol, bisphenol A, bisphenol B, bisphenol Z) in water under solar light irradiation. Compared with single photocatalyst, the optimized sample displayed the reaction rate constant of 0.1606 min⁻¹, which was 69.8, 11.4 and 2.2 times of individual [Bi₆O₆(OH)₃](NO₃)₃∙1.5H₂O, BiOI and BiOIO₃, respectively. The performance improvement was attributed to the inhibition of charge carrier recombination by type II heterojunction formation and the expanded solar capture range caused by the springboard effect of iodine impurity level. The photocatalytic mechanism of I/BiOIO₃/BHN was hole oxidation, followed by·OH oxidation. Besides, the I/BiOIO₃/BHN photocatalyst in bulk structure with micrometer size and high-density could be easily separated and recovered by simple sedimentation, confirming its good application prospect in the wastewater treatment.
Electronic and optical properties of bismuth oxyhalides from ab initio calculations
2021, Materials Science and Engineering: B
So far, semiconductors materials have gained huge attention from researchers because of their superior electrocatalytic activity and employment in different areas. The bismuth oxyhalides BiOXs bulks have great electrocatalytic properties and stability. Astonishingly, few of them have synthesized and there is still a lack of theoretical and experimental data on their bandgap energy, which limits the chance of producing new physical properties. Using density functional theory and beyond with GW and GW BSE approaches, we investigate the electronic and optical properties such as absorption coefficient of bismuth oxyhalides BiOXs (where, X = F, Cl, Br, and I). Our results show that the GW bandgap nature of BiOF is direct, whereas the GW bandgaps of BiOCl, BiOBr, and BiOI are indirect, which is a range from 2.33 eV (BiOI) to 4.04 eV (BiOF). Here, we suggest that can be taken the GW bandgap calculations of BiOCl as a reference to the place of experimental values. Under an external electric field, we succeed to reduce easily and quickly the bandgaps energy of our compounds. Besides, we show that under an external electric field a semiconductor can be changed to a metal with a strong field of more than 0.5 V/Å. In this framework, we have shown that this strategy is better than the incorporation method for engineering in order to find material with a bandgap that we want. We found that the dramatic redshift of the peaks at the BSE level as compared to DFT and RPA indicates strong excitonic effects.
Novel approach for preparation of three-dimensional BiOBr/BiOI hybrid nanocomposites and their removal performance of antibiotics in water
2020, Colloids and Surfaces A: Physicochemical and Engineering Aspects
Herein, a blooming flower-like BiOBr/BiOI was fabricated via solvothermal reduction-ion exchange method and its photocatalytic performance was evaluated by the photocatalytic degradation of levofloxacin hydrochloride in water under visible light irradiation. Morphology, structure, optical properties and some of the underling mechanism were revealed by multifarious characterization techniques, photoelectrochemical measurements, and active substances capture. It was shown that BiOBr/BiOI composite (S6) with molar ratio of 12:1 (BiOBr to BiOI) displayed higher photocatalytic efficiency than pristine BiOBr, BiOI and the composites at other molar ratios. The degradation efficiency of levofloxacin hydrochloride over the optimized composite reached 97 % in 120 min, and even 75.9 % mineralization rate was achieved in 180 min. However, the degradation efficiency was only 48.4 % and 2 % over pristine BiOBr and BiOI, respectively. The enhancement of photocatalytic activity was attributed to the effective separation of photoexcited electron-hole carriers by the formation of BiOBr/BiOI heterojunction. Holes were proved to be the primary active ingredients that degraded levofloxacin hydrochloride. The strategies proposed in this work provide new ideas and methods for the preparation of other related materials and efficient removal of levofloxacin hydrochloride in wastewater.
Correction of band-gap energy and dielectric function of BiOX bulk with GW and BSE
2020, Optik
Citation Excerpt :
These materials are a class of V-VI–VII ternary semiconductors [1]. Further, these compounds all crystallize in the tetragonal matlockite structure [2], which have a tetragonal PbFCl-type structure (space group P4/nmm; No. 129). The bismuth oxyhalides show some promise in the photocatalytic degradation of organic dyes.
Using the DFT method and beyond with GW approximation, we investigate the electronic structures of bismuth oxyhalides BiOXs (where X = F, Cl, Br, and I). The optical properties such as dielectric function and absorption coefficient of BiOXs except BiOI are fully computed with different methods, i.e., DFT, ACFDT in RPA, and with BSE. Our results show that the band-gap nature of BiOF is direct, whereas the band-gaps of BiOCl, BiOBr, and BiOI are indirect. Also, our GW results indicate that the band-gaps of BiOX are very well agreement with the experimental values. Besides, we show that under an external electric field a semiconductor can be changed to a metal with a strong field of more than 0.5 V/Å. Further, we found that the BSE method is the best way to describe the optical properties of BiOXs.
Novel I-doped Bi<inf>12</inf>O<inf>17</inf>Cl<inf>2</inf> photocatalysts with enhanced photocatalytic activity for contaminants removal
2019, Materials Research Bulletin
Novel I-doped Bi₁₂O₁₇Cl₂ photocatalysts have been synthesized using a facile chemical precipitation method and characterized by XRD, XPS, SEM, BET and UV–vis DRS etc. The corresponding results indicate that I⁻ ions enter into the crystal lattices of Bi₁₂O₁₇Cl₂ and replace partial Cl⁻ ions. In addition, the doped I⁻ ions form an impurity level over valence band and extend the visible light absorption ranges of Bi₁₂O₁₇Cl₂. I-doped Bi₁₂O₁₇Cl₂ exhibits much superior visible-light (λ > 420 nm) photocatalytic activity to that of the pure Bi₁₂O₁₇Cl₂ in the methyl orange (MO) and phenol degradation, because a little amount of I⁻ ions can boost the photocharges separation efficiency, which is ensured by photoluminescence spectra, transient photocurrent responses and electrochemical impedance spectra. It is expected that this work opens a new potential pathway to improve the photocatalytic activity of non-stoichiometric ratios bismuth oxyhalide via ions doping strategy.

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Synthesis and characterization of a new series of BiOI1−x−yBrxCly pigments

Abstract

Mod. Plast.

Bull. Am. Ceram. Soc.

Plast. Technol.

Bull. Bismuth Inst.

Synthesis and characterization of a new series of BiOI_1−x−yBr_xCl_y pigments