Mechanistic Aspects of the Bismuth‐Catalysed Oxidation of Epoxides to α‐Diketones

Antoniotti, Sylvain; Duñach, Élisabet

doi:10.1002/ejoc.200400192

Cited by 26 publications

(17 citation statements)

References 17 publications

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“…[126][127][128][129][130] It is also important to get a compound which is stable against decomposition. [131,132] The pioneering efforts aimed at solving the toxicity and instability issues in perovskite solar cells using halide double perovskite therefore incorporated the Bi 3+ along with a monovalent cation Ag + in the B-site. [130] The valence band maximum (VBM) of MAPbI 3 is therefore made up of a mixture of the filled 6s 2 and 5p 6 states of Pb 2+ and I − , while the conduction band minimum (CBM) is made up of the vacant 6p state of Pb 2+ .…”

Section: Optoelectronic Properties Of Halide Double Perovskitesmentioning

confidence: 99%

“…Apart from Pb 2+ , two other main group metal cations Tl + and Bi 3+ can exhibit the 6s 2 6p 0 electronic configuration. However, only Bi 3+ is known to be nontoxic and has been used in organic reactions as a nontoxic additive . The pioneering efforts aimed at solving the toxicity and instability issues in perovskite solar cells using halide double perovskite therefore incorporated the Bi 3+ along with a monovalent cation Ag + in the B‐site .…”

Section: Optoelectronic Properties Of Halide Double Perovskitesmentioning

confidence: 99%

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Progress of Lead‐Free Halide Double Perovskites

Igbari

Wang

Liao

2019

Advanced Energy Materials

397

305

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Although impressive performance has been obtained, PSCs are still far from commercial or real-life availability due to serious issues such as toxicity [15,16] and poor stability to heat, [17] oxygen, [18] moisture, [19,20] electric field, [21] and light. [18,22] The toxic nature of hybrid organic-inorganic lead halide perovskites has been traced to the presence of Pb in its chemical composition. [15,16,[23][24][25] Pb 2+ readily dissolves in water (e.g., rain water) to form a toxic solution capable of causing serious environmental pollution, harmful to human beings and the ecosystem. Besides their sensitivity to moisture, oxygen, light, electric field, or thermal stress, an existing self-degradation pathway [26,27] is also a big issue in hybrid organic-inorganic lead halide perovskites. Mixed-halide and mixed-cation perovskites have been investigated to address these issues. [28][29][30][31][32] The group IV elements, tin (Sn) [23,[33][34][35] and germanium (Ge), [34,36] have been employed as the replacements for Pb. However, the device performance through this approach has fallen short of the Pb-based ones. For example, the PCEs reported for Sn-based perovskite solar cells are usually less than 10%. [23,[33][34][35][37][38][39][40] In addition, the easy oxidation of Sn and Ge from the +2 state to the +4 state due to their high energy 5s and 4s orbitals makes them less promising for application in stable and long-term PSCs. [41] High throughput calculations also demonstrate that these substitutions are likely to compromise the ideal optoelectronic properties of MAPbI 3 . [42,43] Furthermore, low dimensional (e.g., 2D, 1D, and 0D) perovskites have also been used to address the stability issues in PSCs. [44][45][46][47][48] Recently, a stabilized PCE of 21.7% resulting from a 2D/3D bilayer PSC was reported. [49] However, the highest certified PCE in a 2D-only planar PSC is 15.3%, [50] which is far below that of their 3D perovskite-based counterparts. It thus stimulates the interest to develop new classes of materials which can solve the issues of toxicity and stability while still maintaining the fascinating properties of lead-based perovskite materials.Recent theoretical calculations demonstrate that a halide double perovskite structure, A 2 B′B″X 6 , which could be formed through a replacement of two toxic Pb 2+ in the crystal lattice with a pair of nontoxic heterovalent (i.e., monovalent and trivalent) metal cations, is a promising alternative to realize high-performance, lead-free, and stable PSCs. [51,52] Although, spectroscopic limited maximum efficiency (SLME) calculations revealed an efficiency limit less than 8% for the most prominent member www.advancedsciencenews.com double perovskites with a vacancy ordered structure. [88] In particular, the unit cell axis of Cs 2 AgBiBr 6 is given to be ≈11.25 Å, [25] which is two times larger than that of MAPbBr 3 (≈5.92 Å). [89] Both Ag + and Bi 3+ occupy the B-site of the crystal lattice with slightly varied metal-halide bond lengths. The dissimilar bond lengths st...

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Section: Optoelectronic Properties Of Halide Double Perovskitesmentioning

confidence: 99%

Section: Optoelectronic Properties Of Halide Double Perovskitesmentioning

confidence: 99%

Progress of Lead‐Free Halide Double Perovskites

Igbari

Wang

Liao

2019

Advanced Energy Materials

397

305

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“…34,35 This interesting phenomenon prompted us to examine the behavior of various metals of low standard reduction potential under these oxidative conditions.…”

Section: Oxidative Dissolution Of Metallic Powders In the Presence Ofmentioning

confidence: 99%

“…During mechanistic studies on the oxidation of internal epoxides by metallic bismuth in the presence of triflic acid, we observed that the bismuth metal powder was totally dissolved in DMSO at 100°C under an atmospheric pressure of O 2 to form bismuth(III) triflate solvated by DMSO (Scheme 3). 34,35 This interesting phenomenon prompted us to examine the behavior of various metals of low standard reduction potential under these oxidative conditions.…”

Section: Oxidative Dissolution Of Metallic Powders In the Presence Of Superacidsmentioning

confidence: 99%

Electrophilic Functionalization of Non-Activated Olefins Catalyzed by Lewis Superacids

Antoniotti¹,

Poulain-Martini²,

Duñach³

2010

Synlett

Self Cite

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“…[67] Even having the heavy metal status, bismuth and its compounds have attracted organic chemists, due to their relatively non-toxicity, ease of handling and non-corrosive nature. [68] Bismuth analogues promote versatile organic transformations most importantly the oxidation of aziridines [69] and epoxides. [70] They are suitable as mild Lewis acid catalysts for organic transformation.…”

Section: Bi 2 O 3 /Zromentioning

confidence: 99%

Our Contributions in Synthesis of Diverse Heterocyclic Scaffolds by Using Mixed Oxides as Heterogeneous Catalysts

Bhaskaruni

Gangu

Maddila

et al. 2018

The Chemical Record

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This personal account mainly introduces and reviews our recent contributions in developing different catalyst materials involving mixed oxides and their scope as renewable catalysts in multicomponent reactions to synthesize various novel heterocyclic scaffolds under green conditions. The application of various mixed oxides and their composites in the organic synthesis is emphasized through this review, in order to reveal the versatility, scope and importance of mixed oxides and their interactions during the reaction. We have also briefed the limitations of mixed oxides as catalysts, to put forward the broader prospective in the field.

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Mechanistic Aspects of the Bismuth‐Catalysed Oxidation of Epoxides to α‐Diketones

Cited by 26 publications

References 17 publications

Progress of Lead‐Free Halide Double Perovskites

Progress of Lead‐Free Halide Double Perovskites

Electrophilic Functionalization of Non-Activated Olefins Catalyzed by Lewis Superacids

Our Contributions in Synthesis of Diverse Heterocyclic Scaffolds by Using Mixed Oxides as Heterogeneous Catalysts

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