metastable compounds
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2022 ◽  
Vol 962 (1) ◽  
pp. 012058
Author(s):  
A G Sekisov ◽  
T G Konareva ◽  
A Yu Lavrov ◽  
V Yu Burov ◽  
E S Emirziadi

Abstract The article deals with the data of theoretical and experimental studies of the processes of activation gold leaching using reactive peroxide carbonate compounds, obtained by electrophotochemical treatment of solutions of initial reagents of the corresponding composition, in the composition of reagent complexes. The obtained results of the experiments on the interaction of various carbonate and peroxide-carbonate compounds with sodium cyanide in the process of mixing activated and non-activated solutions with aqueous cyanide solutions in different order definitely prove that supramolecular percarbonate-cyanide compounds are being formed in them. It has been established that these activated solutions, prepared on the basis of the initial hydrocarbonate ones, contain metastable compounds that provide a higher rate of gold extraction from crude minerals than standard aqueous cyanic solutions of the same initial concentration.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Silke Notter ◽  
Carsten Donsbach ◽  
Claus Feldmann

Abstract The iodido bismuthates [Bi(18-crown-6)I2][BiI4] (1) and [Bi(18-crown-6)I2][Bi3I10] (2), the neutral complex [Bi(C6H14O4)I3](18-crown-6) (3) as well as the polyiodides [Bi(18-crown-6)I2][I5](18-crown-6) (4), [Bi(18-crown-6)I2]2[I14] (5) and [Bi(18-crown-6)I2]2[I19] (6) were prepared by reaction of BiI3, 18-crown-6, and I2 at T = 60–120 °C. The compounds 1–5 were prepared in [n-Bu3MeN][N(Tf)2] as an ionic liquid ([n-Bu3MeN]: tributylmethylammonium, [N(Tf)2]: bis(trifluoromethylsulfonyl)imide), whereas 6 was obtained only by direct reaction of the starting materials. The title compounds exhibit two different constitutions of the [Bi(18-crown-6)I2]+ cation as well as a non-charged, molecular [Bi(C6H14O4)I3] unit with a triethylene glycol ligand generated in situ by cleavage of the crown ether. Infinite chain-like [ BiI 2 / 1 I 4 / 2 ] − ∞ 1 ${}_{\infty }{}^{1}[{{\text{BiI}}_{2/1}{\text{I}}_{4/2}]}^{-}$ and [ Bi 6 I 18 / 1 I 4 / 2 ∞ 1 ] − ${{}_{\infty }{}^{1}[{\text{Bi}}_{6}{\text{I}}_{18/1}{\text{I}}_{4/2}]}^{-}$ anions occur in 1 and 2, whereas various polyiodide anions (e.g. [I3]−, [I5]−, [I7]−, [I9]−) with partly complex interaction are observed in 4, 5, and 6. The title compounds were characterized by single-crystal X-ray diffraction analysis and infrared spectroscopy. In the case of 1 and 2, the optical band gap was determined to be E g  = 1.91 and 1.62 eV, respectively. Especially, the ionic-liquid-based synthesis affords the different metastable compounds with variable composition and structure in a narrow temperature range.


Materials ◽  
2021 ◽  
Vol 14 (15) ◽  
pp. 4245
Author(s):  
Yann Le Godec ◽  
Alexandre Courac

High-pressure synthesis (which refers to pressure synthesis in the range of 1 to several GPa) adds a promising additional dimension for exploration of compounds that are inaccessible to traditional chemical methods and can lead to new industrially outstanding materials. It is nowadays a vast exciting field of industrial and academic research opening up new frontiers. In this context, an emerging and important methodology for the rapid exploration of composition-pressure-temperature-time space is the in situ method by synchrotron X-ray diffraction. This review introduces the latest advances of high-pressure devices that are adapted to X-ray diffraction in synchrotrons. It focuses particularly on the “large volume” presses (able to compress the volume above several mm3 to pressure higher than several GPa) designed for in situ exploration and that are suitable for discovering and scaling the stable or metastable compounds under “traditional” industrial pressure range (3–8 GPa). We illustrated the power of such methodology by (i) two classical examples of “reference” superhard high-pressure materials, diamond and cubic boron nitride c-BN; and (ii) recent successful in situ high-pressure syntheses of light-element compounds that allowed expanding the domain of possible application high-pressure materials toward solar optoelectronic and infra-red photonics. Finally, in the last section, we summarize some perspectives regarding the current challenges and future directions in which the field of in situ high-pressure synthesis in industrial pressure scale may have great breakthroughs in the next years.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Shunsuke Sasaki ◽  
Maria Teresa Caldes ◽  
Catherine Guillot-Deudon ◽  
Isabelle Braems ◽  
Gwladys Steciuk ◽  
...  

AbstractDesigning and synthesising new metastable compounds is a major challenge of today’s material science. While exploration of metastable oxides has seen decades-long advancement thanks to the topochemical deintercalation of oxygen as recently spotlighted with the discovery of nickelate superconductor, such unique synthetic pathway has not yet been found for chalcogenide compounds. Here we combine an original soft chemistry approach, structure prediction calculations and advanced electron microscopy techniques to demonstrate the topochemical deintercalation/reintercalation of sulfur in a layered oxychalcogenide leading to the design of novel metastable phases. We demonstrate that La2O2S2 may react with monovalent metals to produce sulfur-deintercalated metastable phases La2O2S1.5 and oA-La2O2S whose lamellar structures were predicted thanks to an evolutionary structure-prediction algorithm. This study paves the way to unexplored topochemistry of mobile chalcogen anions.


2021 ◽  
Author(s):  
Veronika Heinl ◽  
Andreas Seitz ◽  
Gabor Balazs ◽  
Michael Seidl ◽  
Manfred Scheer

Transfer reagents are useful tools in chemistry to access metastable compounds. The reaction of [Cp''2ZrCl2] with KSb(SiMe3)2 leads to the formation of the novel polyantimony triple decker complex [(Cp''Zr)2(µ,ƞ1:1:1:1:1:1 Sb6)]...


Surface ◽  
2020 ◽  
Vol 12(27) ◽  
pp. 193-230
Author(s):  
А. R. Zheleznyak ◽  
◽  
О. М. Bakalinska ◽  
А. V. Brichka ◽  
G. O. Kalenyuk ◽  
...  

The prevalence of tin compounds, economic affordability and non-toxicity determine its wide range of applications. Modern scientific literature on the properties, methods of preparation and application of tin nanooxide is analyzes in review. Its main characteristics and structural features are described. The ability of tin cations to be in two oxidation states, the ease of reduction of Sn+4 to Sn+2 and reverse oxidation, determines the redox properties of the SnO2 surface. In addition to stable oxides Sn4+ and Sn2,+ the existence of a homologous series of Snn+1O2n metastable compounds is assumed. It is proved that four-coordinated Sn+2 cations on the SnO2 surface can coexist only with oxygen vacancies in the immediate environment. Such cationic sites have the properties of strong Lewis acids and are highly reactive. Computer simulation of the SnO2 crystal surface allows us to propose a number of catalytic activity of SnO2 surfaces: (110) < (001) < (100) < (101). Preparation methods and synthesis parameters (nature and type of precursor, stabilizing agent and solvent, duration and temperature of the reaction, pH of the reaction mixture, etc.) determine the physicochemical properties of nanoparticles (shape, size, morphology and degree of crystallinity). The main (sol-gel, precipitation and coprecipitation, CVD, spray pyrolysis, hydrothermal, “green”) and less common (detonation, electric discharge) methods of nano-SnO2 obtaining are analyzed in the work. A variety of methods of synthesis and conditions makes it possible to obtain SnO2 nanoparticles with desired properties, which determine the activity of tin oxide in redox reactions, namely: nanosize and morphology of particles with prevalence of the most reactive faces - (100) і (101). Among the methods that do not require complex hardware design, one can dwell on the methods of sol-gel, "green" and coprecipitation. Tin oxide is traditionally used as an abrasive for polishing metal, glass and ceramic products. The transition to nanosized particles allows this material to reversibly absorb and release oxygen, which has determined its use in the design of gas-sensitive and biosensors, the creation of solar cells, fuel cells, lithium-ion batteries, oxidation catalysts, transparent and photoconductors. The multivalence and the presence of oxygen vacancies on the surface of tin oxide nanoparticles, the ease and speed of penetration into the cell membrane give nano-SnO2 properties of medicinal preparations, which makes it possible to use it in biomedical technologies for the treatment of diseases associated with oxidative stress lesions. The size, concentration of nanoparticles and modification of their surface are the key factors of influence, which usually intensify the antimicrobial, antibacterial, antitumor and antioxidant activity of the material.


2020 ◽  
Vol 49 (48) ◽  
pp. 17584-17593
Author(s):  
Laura Caggiu ◽  
Antonio Iacomini ◽  
Claudio Pistidda ◽  
Valeria Farina ◽  
Nina Senes ◽  
...  

In situ synchrotron and conventional XRD patterns were solved for the phase developed at 700 °C with the Amm2 orthorhombic space group, lattice parameters a = 21.187 Å; b = 3.827 Å; c = 19.377 Å; β = 119.83° and chemical composition V4Nb20O60 (ρ = 4.09 g cm−3).


2019 ◽  
Author(s):  
Hassen Jaafar ◽  
Mohieddine Abdellaoui

The use of mechanical alloying in this work leads to a solid solution Mg0.33Al0.66 instead of Laves phase MgAl2. Monosubstituted alloy Mg0.33Al0.63Si0.03 was obtained in good yield after 20 hours mechanical alloying with shock power of 6.5 W/g. Current work in progress aims to study the thermodynamic hydrogenation properties of these metastable compounds and explore different substitution for possible adaptation serving stabilized solid-Hydrogen as bulk reservoir in Fuel Cells or Ni-MH batteries.


2019 ◽  
Author(s):  
Hassen Jaafar ◽  
Mohieddine Abdellaoui

The use of mechanical alloying in this work leads to a solid solution Mg0.33Al0.66 instead of Laves phase MgAl2. Monosubstituted alloy Mg0.33Al0.63Si0.03 was obtained in good yield after 20 hours mechanical alloying with shock power of 6.5 W/g. Current work in progress aims to study the thermodynamic hydrogenation properties of these metastable compounds and explore different substitution for possible adaptation serving stabilized solid-Hydrogen as bulk reservoir in Fuel Cells or Ni-MH batteries.


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