Nanoscaled Metal Borides and Phosphides: Recent Developments and Perspectives

Carenco, Sophie; Portehault, David; Boissière, Cédric; Mézailles, Nicolas; Sánchez, Clément

doi:10.1021/cr400020d

Cited by 897 publications

(765 citation statements)

References 1,158 publications

Supporting

Mentioning

748

Contrasting

Unclassified

Order By: Relevance

“…Li is likely either intercalated into the Zn seeds or amorphous Sb. Powder XRD data of a '0 min' sample (removed and isolated immediately upon injection) does 55,[57][58][59][60][61][62][63] Scheme 2. Mechanism of formation h*-LiZnSb.…”

Section: Resultsmentioning

confidence: 99%

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

et al. 2018

View full text Add to dashboard Cite

Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of syn-thetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Further, we find one of the ternary phases adopts a variant of the previously observed hexagonal LiZnSb struc-ture. Our results demonstrate the utility of low temperature solution phase-soft synthesis-methods in accessing and mining a rich phase space. We anticipate that this work will motivate further exploration of multinary I-II-V compounds, as well as encourage similarly thorough investigations of related Zintl systems by solution phase methods. Disciplines Materials ChemistryComments "This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Chemistry of Materials, copyright © American Chemical Society after peer review. To access the final edited and published work see http://dx.doi.org/10.1021/acs.chemmater.8b02910. ABSTRACT: Soft chemistry methods offer the possibility of synthesizing metastable and kinetic products that are unobtainable through thermodynamically-controlled, high-temperature reactions. A recent solution-phase exploration of Li-Zn-Sb phase space revealed a previously unknown cubic half-Heusler MgAgAs-type LiZnSb polytype. Interestingly, this new cubic phase was calculated to be the most thermodynamically stable, despite prior literature reporting only two other ternary phases (the hexagonal half-Heusler LiGaGe-type LiZnSb, and the full-Heusler Li2ZnSb). This surprising discovery, coupled with the intriguing optoelectronic and transport properties of many antimony containing Zintl phases, required a thorough exploration of synthetic parameters. Here, we systematically study the effects that different precursor concentrations, injection order, nucleation and growth temperatures, and reaction time have on the solution-phase synthesis of these materials. By doing so, we identify conditions that selectively yield several unique ternary (c-LiZnSb vs. h*-LiZnSb), binary (ZnSb vs. Zn8Sb7), and metallic (Zn, Sb) products. Furt...

show abstract

Section: Resultsmentioning

confidence: 99%

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Examples include its use as a substrate for group III nitride semiconductors in optoelectronic devices [1][2][3][4][5] , as support material for low-temperature fuel cells 6,7 , and as a hydrogen storage medium 8 . Difficulties associated with synthesis, however, have hindered broad adoption of the material -production of high-density ZrB 2 typically requires both extremely high temperature and pressure 9 because of its high melting point and stability.…”

mentioning

confidence: 99%

“…Difficulties associated with synthesis, however, have hindered broad adoption of the material -production of high-density ZrB 2 typically requires both extremely high temperature and pressure 9 because of its high melting point and stability. Viable synthesis methods of ZrB 2 have been a topic of intense investigation for decades 5,9,10 . Additives such as carbon have been shown to improve the processability of ZrB 2 .…”

mentioning

confidence: 99%

Kinetic Role of Carbon in Solid-State Synthesis of Zirconium Diboride using Nanolaminates: Nanocalorimetry Experiments and First-Principles Calculations

et al. 2015

View full text Add to dashboard Cite

Reactive nano-laminates afford a promising route for the low-temperature synthesis of zirconium diboride, an ultrahigh-temperature ceramic with metallic properties. Although the addition of carbon is known to facilitate sintering of ZrB 2 , its effect on the kinetics of the formation reaction has not been elucidated. We have employed a combined approach of nanocalorimetry and first-principles theoretical studies to investigate the kinetic role of carbon in the synthesis of ZrB 2 using B 4 C/Zr reactive nano-laminates. Structural characterization of the laminates by XRD and TEM reveal that the reaction proceeds via inter-diffusion of the B 4 C and Zr layers, which produces an amorphous Zr 3 B 4 C alloy. This amorphous alloy then crystallizes to form a super-saturated ZrB 2 (C) compound. A kinetic analysis shows that carbon lowers the energy barriers for both inter-diffusion and crystallization by more than 20%. Energetic calculations based on first-principles modeling suggest that the reduction of the diffusion barrier may be attributed to the stronger bonding between Zr and C as compared to the bonding between Zr and B.

show abstract

“…Better results were obtained using 4, a long-chain (n-octyl) alkyl phosphine oxide often used as stabiliser for metal nanoparticle synthesis [20], or as extraction agent, especially for uranium [21]. After optimisation of the reaction conditions (Entries [15][16][17][18][19][20][21][22], the highest conversion (87%) was obtained with 15 equiv.…”

Section: Discussionmentioning

confidence: 99%

“…After optimisation of the reaction conditions (Entries [15][16][17][18][19][20][21][22], the highest conversion (87%) was obtained with 15 equiv. PHMS at 220 • C after 7 h (Entry 20).…”

Section: Discussionmentioning

confidence: 99%

Metal-Free Reduction of Phosphine Oxides Using Polymethylhydrosiloxane

et al. 2016

View full text Add to dashboard Cite

Abstract:A simple protocol is presented here for the use of inexpensive polymethylhydrosiloxane (PMHS), a waste product of the silicon industry, as stoichiometric reducing agent for phosphine oxides to phosphines, a highly desirable reaction to recover P-based ligands from their spent form. The reactions were studied by screening parameters, such as substrate to reductant ratio, temperature and reaction time, achieving good conversions and selectivities.

show abstract

Nanoscaled Metal Borides and Phosphides: Recent Developments and Perspectives

Abstract: International audienceno abstrac

Cited by 897 publications

References 1,158 publications

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

Expanding the I–II–V Phase Space: Soft Synthesis of Polytypic Ternary and Binary Zinc Antimonides

Kinetic Role of Carbon in Solid-State Synthesis of Zirconium Diboride using Nanolaminates: Nanocalorimetry Experiments and First-Principles Calculations

Metal-Free Reduction of Phosphine Oxides Using Polymethylhydrosiloxane

Contact Info

Product

Resources

About