Special Issue "Boron-Based (Nano-)Materials: Fundamentals and Applications"

A special issue of Crystals (ISSN 2073-4352).

Deadline for manuscript submissions: closed (31 March 2016)

Special Issue Editors

Guest Editor
Prof. Dr. Umit B. Demirci

IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universite Montpellier 2, Place E. Bataillon, F-34095, Montpellier, France
Website | E-Mail
Fax: +33(0)4.67.14.91.19
Interests: Boranes; Boron- and nitrogen-based materials; Chemical hydrogen storage; Hydrolytic and thermolytic dehydrogenation; Heterogeneous (metal) catalysis
Guest Editor
Prof. Dr. Philippe Miele

IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM), Université of Montpellier, Place E. Bataillon, F-34095, Montpellier, France
Website | E-Mail
Interests: boron nitride; fibers; nanotubes; nanostructured ceramics; porous ceramics; hierarchical materials; molecular an polymeric precursors of non-oxide ceramics; borazine; borazine-based preceramic polymers; boron-based materials for hydrogen storage
Guest Editor
Dr. Pascal G. Yot

ICGM (Institut Charles Gerhardt Montpellier), UMR 5253 (UM-CNRS-ENSCM), Universite de Montpellier, CC 15005, Place Eugène Bataillon, F-34095, Montpellier cedex 05, France
Website | E-Mail
Interests: Diffractions Techniques; Structure determination; Structure-Properties Relations; Mechanical and thermal behaviour; Boron based materials

Special Issue Information

Dear Colleagues,

As leading scientists in the field, we all agree that among the light elements boron is rather unique. Since the early 19th century, it has fascinated generations of scientists. In the 20th century, it has shown to be versatile, having been widely used in many areas of application including enamels, metallurgy, ceramics, synthetic organic chemistry, fertilizers, fungicides, detergents, soaps, antiseptics, cosmetics, and so forth. In the past decades, boron has been an important element in materials science through the emergence of new and innovative application prospects. Accordingly, the present Special Issue is dedicated to new boron-based (nano-)materials and emphasizes recent advances on fundamentals and application prospects.

In this context, the main focus of the forthcoming “Boron-Based Materials: Fundamentals and Applications” Special Issue is to present a comprehensive overview of the new developments in the field, while focusing on research and review articles about crystalline boron-based (nano-)materials for medicine (e.g., radioisotope and boron neutron capture therapy), health and nutrition, electronics, energy (e.g., hydrogen, fuel cell and nuclear energy), organic and inorganic chemistry, catalysis, ceramics, and any other relevant area of application.

It is our pleasure to invite you to submit a manuscript for this Special Issue. Full papers, communications, and reviews are all welcome.

Prof. Dr. Umit B. Demirci
Prof. Dr. Philippe Miele
Dr. Pascal G. Yot
Guest Editors

Manuscript Submission Information

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Keywords

  • Boron science
  • Boron-based materials
  • Nanomaterials
  • Fundamentals
  • Applications

Published Papers (10 papers)

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Editorial

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Open AccessEditorial Boron-Based (Nano-)Materials: Fundamentals and Applications
Crystals 2016, 6(9), 118; doi:10.3390/cryst6090118
Received: 6 September 2016 / Accepted: 13 September 2016 / Published: 19 September 2016
PDF Full-text (1396 KB) | HTML Full-text | XML Full-text
Abstract
The boron (Z = 5) element is unique. Boron-based (nano-)materials are equally unique. Accordingly, the present special issue is dedicated to crystalline boron-based (nano-)materials and gathers a series of nine review and research articles dealing with different boron-based compounds. Boranes, borohydrides, polyhedral boranes
[...] Read more.
The boron (Z = 5) element is unique. Boron-based (nano-)materials are equally unique. Accordingly, the present special issue is dedicated to crystalline boron-based (nano-)materials and gathers a series of nine review and research articles dealing with different boron-based compounds. Boranes, borohydrides, polyhedral boranes and carboranes, boronate anions/ligands, boron nitride (hexagonal structure), and elemental boron are considered. Importantly, large sections are dedicated to fundamentals, with a special focus on crystal structures. The application potentials are widely discussed on the basis of the materials’ physical and chemical properties. It stands out that crystalline boron-based (nano-)materials have many technological opportunities in fields such as energy storage, gas sorption (depollution), medicine, and optical and electronic devices. The present special issue is further evidence of the wealth of boron science, especially in terms of crystalline (nano-)materials. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
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Figure 1

Research

Jump to: Editorial, Review

Open AccessArticle Hydrogen Desorption Properties of Bulk and Nanoconfined LiBH4-NaAlH4
Crystals 2016, 6(6), 70; doi:10.3390/cryst6060070
Received: 10 April 2016 / Revised: 8 June 2016 / Accepted: 9 June 2016 / Published: 20 June 2016
Cited by 2 | PDF Full-text (12231 KB) | HTML Full-text | XML Full-text
Abstract
Nanoconfinement of 2LiBH4-NaAlH4 into a mesoporous carbon aerogel scaffold with a pore size, BET surface area and total pore volume of Dmax = 30 nm, SBET = 689 m2/g and Vtot = 1.21 mL/g, respectively
[...] Read more.
Nanoconfinement of 2LiBH4-NaAlH4 into a mesoporous carbon aerogel scaffold with a pore size, BET surface area and total pore volume of Dmax = 30 nm, SBET = 689 m2/g and Vtot = 1.21 mL/g, respectively is investigated. Nanoconfinement of 2LiBH4-NaAlH4 facilitates a reduction in the temperature of the hydrogen release by 132 °C, compared to that of bulk 2LiBH4-NaAlH4 and the onset of hydrogen release is below 100 °C. The reversible hydrogen storage capacity is also significantly improved for the nanoconfined sample, maintaining 83% of the initial hydrogen content after three cycles compared to 47% for that of the bulk sample. During nanoconfinement, LiBH4 and NaAlH4 reacts to form LiAlH4 and NaBH4 and the final dehydrogenation products, obtained at 481 °C are LiH, LiAl, AlB2 and Al. After rehydrogenation of the nanoconfined sample at T = 400 °C and p(H2) = 126 bar, amorphous NaBH4 is recovered along with unreacted LiH, AlB2 and Al and suggests that NaBH4 is the main compound that can reversibly release and uptake hydrogen. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
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Open AccessArticle Influence of Defects in Boron Nitride Nanotubes in the Adsorption of Molecules. Insights from B3LYP-D2* Periodic Simulations
Crystals 2016, 6(5), 63; doi:10.3390/cryst6050063
Received: 27 April 2016 / Revised: 11 May 2016 / Accepted: 12 May 2016 / Published: 20 May 2016
Cited by 5 | PDF Full-text (1678 KB) | HTML Full-text | XML Full-text
Abstract
The adsorption of H2O, NH3 and HCOOH as polar molecules and C6H6 and CH4 as non-polar ones on a series of zig-zag (6,0) single-walled boron nitride nanotubes (BNNTs) both being defect-free (P_BNNT) and containing defects at
[...] Read more.
The adsorption of H2O, NH3 and HCOOH as polar molecules and C6H6 and CH4 as non-polar ones on a series of zig-zag (6,0) single-walled boron nitride nanotubes (BNNTs) both being defect-free (P_BNNT) and containing defects at the nanotube walls has been studied by means of B3LYP-D2* periodic calculations. We focused on defects derived from monovacancies of B (N-rich_BNNT) and N (B-rich_BNNT) atoms and also on Stone-Wales defects (SW_BNNT). The adsorption of polar molecules with defective BNNTs is generally based on dative interactions and H-bonding, and their adsorption energies strongly depend on the type of BNNT. N-rich_BNNT is the most reactive nanotube towards adsorption of polar molecules, as in all cases deprotonation of the polar molecules is spontaneously given upon adsorption. The strength in the adsorption energies is followed by B-rich_BNNT, SW_BNNT and P_BNNT. Adsorption of non-polar molecules is mainly dictated by dispersion interactions, and, accordingly, the adsorption energies are almost constant for a given molecule irrespective of the type of nanotube. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
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Open AccessArticle In situ Synchrotron X-ray Thermodiffraction of Boranes
Crystals 2016, 6(2), 16; doi:10.3390/cryst6020016
Received: 19 December 2015 / Revised: 15 January 2016 / Accepted: 21 January 2016 / Published: 25 January 2016
Cited by 3 | PDF Full-text (1707 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Boranes of low molecular weight are crystalline materials that have been much investigated over the past decade in the field of chemical hydrogen storage. In the present work, six of them have been selected to be studied by in situ synchrotron X-ray thermodiffraction.
[...] Read more.
Boranes of low molecular weight are crystalline materials that have been much investigated over the past decade in the field of chemical hydrogen storage. In the present work, six of them have been selected to be studied by in situ synchrotron X-ray thermodiffraction. The selected boranes are ammonia borane NH3BH3 (AB), hydrazine borane N2H4BH3 (HB), hydrazine bisborane N2H4(BH3)2 (HBB), lithium LiN2H3BH3 (LiHB) and sodium NaN2H3BH3 (NaHB) hydrazinidoboranes, and sodium triborane NaB3H8 (STB). They are first investigated separately over a wide range of temperature (80–300 K), and subsequently compared. Differences in crystal structures, the existence of phase transition, evolutions of unit cell parameters and volumes, and variation of coefficients of thermal expansion can be observed. With respect to AB, HB and HBB, the differences are mainly explained in terms of molecule size, conformation and motion (degree of freedom) of the chemical groups (NH3, N2H4, BH3). With respect to LiHB, NaHB and STB, the differences are explained by a stabilization effect favored by the alkali cations via M···H interactions with four to five borane anions. The main results are presented and discussed herein. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
Open AccessArticle Influence of Boron on Initial Austenite Grain Size and Hot Deformation Behavior of Boron Microalloyed Steels
Crystals 2015, 5(4), 592-607; doi:10.3390/cryst5040592
Received: 11 October 2015 / Accepted: 16 November 2015 / Published: 24 November 2015
Cited by 1 | PDF Full-text (2341 KB) | HTML Full-text | XML Full-text
Abstract
The initial austenite grain size of boron microalloyed steel with three different amounts of boron (20, 40, and 60 ppm) was investigated under different heating temperatures (1150, 1100, and 1050 °C), and hot compression tests of samples in a wide range of temperature
[...] Read more.
The initial austenite grain size of boron microalloyed steel with three different amounts of boron (20, 40, and 60 ppm) was investigated under different heating temperatures (1150, 1100, and 1050 °C), and hot compression tests of samples in a wide range of temperature (900–1100 °C) and strain rate (0.1–10 s−1) were conducted. It was found that the initial austenite grain size increases with increasing temperature and boron content. The flow stress decreased with increasing boron content at lower strain rates. The flow stress constitutive equation of hot deformation was developed for the experimental steels; results showed that boron addition has the trend to reduce the hot deformation activation energy. The characteristic points of the flow curves were analyzed. Results revealed that the peak and critical stress decreased in response to an increase of boron content. The work-hardening behavior of both steels was investigated, and it was found that boron addition can decrease the work-hardening rate when strained at lower strain rates. On the contrary, peak and critical strains increased as boron content increased, indicating that boron has the ability to delay the onset of dynamic recrystallization. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)

Review

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Open AccessReview Mono- and Bimetalic Amidoboranes
Crystals 2016, 6(8), 88; doi:10.3390/cryst6080088
Received: 13 May 2016 / Revised: 13 July 2016 / Accepted: 20 July 2016 / Published: 5 August 2016
Cited by 5 | PDF Full-text (4185 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In this review, we present an overview on metal amidoboranes, which have recently been considered as hydrogen storage materials for fueling of the low temperature fuel cells. We focus on amidoborane salts containing only metal cations and amidoborate anions. During the last decades,
[...] Read more.
In this review, we present an overview on metal amidoboranes, which have recently been considered as hydrogen storage materials for fueling of the low temperature fuel cells. We focus on amidoborane salts containing only metal cations and amidoborate anions. During the last decades, 19 new compounds from this group were described in the literature. We provide a summary of various physical and chemical properties of amidoborane compounds reported up to date. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
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Open AccessReview Silver and Copper Complexes with closo-Polyhedral Borane, Carborane and Metallacarborane Anions: Synthesis and X-ray Structure
Crystals 2016, 6(5), 60; doi:10.3390/cryst6050060
Received: 31 March 2016 / Revised: 19 April 2016 / Accepted: 20 April 2016 / Published: 20 May 2016
Cited by 9 | PDF Full-text (36438 KB) | HTML Full-text | XML Full-text
Abstract
Synthesis and structure of silver and copper salts and complexes with polyhedral boron hydride anions, including closo-decaborate [B10H10]2−, closo-dodecaborate [B12H12]2−, 1-carba-closo- decaborate [1-CB9H10]
[...] Read more.
Synthesis and structure of silver and copper salts and complexes with polyhedral boron hydride anions, including closo-decaborate [B10H10]2−, closo-dodecaborate [B12H12]2−, 1-carba-closo- decaborate [1-CB9H10], carba-closo-dodecaborate [CB11H12], and cobalt bis(dicarbollide) [3,3′-Co(1,2-C2B9H11)2] anions and their derivatives, are reviewed. The complexes demonstrate a wide variety of structural types, relating to both the metal coordination environment and coordination modes of boron hydride anions. The latter can range from strong coordination via the polyhedron triangular face including formation of 3c-2e MHB bonds in the case of the [B10H10]2− dianion, the structure of which contains two four-coordinated boron atoms, to very weak M…H interactions with the hydride atoms in the case of bulky [3,3′-Co(1,2-C2B9H11)2] monoanion. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
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Open AccessReview How to Increase the h-BN Crystallinity of Microfilms and Self-Standing Nanosheets: A Review of the Different Strategies Using the PDCs Route
Crystals 2016, 6(5), 55; doi:10.3390/cryst6050055
Received: 7 April 2016 / Revised: 1 May 2016 / Accepted: 3 May 2016 / Published: 13 May 2016
Cited by 4 | PDF Full-text (10332 KB) | HTML Full-text | XML Full-text
Abstract
Hexagonal boron nitride (h-BN) is a well-known material whose use is almost restricted to lubricating applications in domains ranging from metallurgy to cosmetics. Howover, h-BN displays many other interesting properties, opening new perspectives for other engineering applications, such as as a solid lubricant
[...] Read more.
Hexagonal boron nitride (h-BN) is a well-known material whose use is almost restricted to lubricating applications in domains ranging from metallurgy to cosmetics. Howover, h-BN displays many other interesting properties, opening new perspectives for other engineering applications, such as as a solid lubricant in aeronautics, as the perfect substrate to graphene for electronic devices, etc. However, all these promising developments require tailored h-BN shapes displaying a high level of crystallization, ensuring its properties for the long term. Here, we developed three strategies, all associated with the Polymer Derived Ceramics (PDCs) route, to prepare highly crystallized supported thick coatings and self-standing nanosheets. The first strategy concerns the innovative implementation of a Rapid Thermal Annealing to prepare micrometric h-BN coatings on thermal sensitive substrates. Compared to conventional treatment the crystallization of h-BN has successfully lowered to about 300 °C. The second strategy consists of an additivation of the used polymer precursor. Effect of lithium nitride as a crystallization promoter was investigated lowering the onset crystallization temperature from 1400 °C (traditionally) to 1000 °C. This novel synthetic route allows preparing self-standing highly crystallized h-BN nanolayers. Finally, the third strategy is based on a unique combination of the PDCs route with Spark Plasma Sintering to profit of both approaches. This original method leads to large and well-crystallized flakes available for a subsequent exfoliation. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
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Open AccessReview N,O-Type Carborane-Based Materials
Crystals 2016, 6(5), 50; doi:10.3390/cryst6050050
Received: 29 March 2016 / Revised: 25 April 2016 / Accepted: 27 April 2016 / Published: 4 May 2016
Cited by 4 | PDF Full-text (8083 KB) | HTML Full-text | XML Full-text
Abstract
This review summarizes the synthesis and coordination chemistry of a series of carboranyl ligands containing N,O donors. Such carborane-based ligands are scarcely reported in the literature when compared to other heteroatom-containing donors. The synthetic routes for metal complexes of these N,O-type carborane ligands
[...] Read more.
This review summarizes the synthesis and coordination chemistry of a series of carboranyl ligands containing N,O donors. Such carborane-based ligands are scarcely reported in the literature when compared to other heteroatom-containing donors. The synthetic routes for metal complexes of these N,O-type carborane ligands are summarized and the properties of such complexes are described in detail. Particular attention is paid to the effect that the incorporation of carboranes has into the coordination chemistry of the otherwise carbon-based ligands and the properties of such materials. The reported complexes show a variety of properties such as those used in magnetic, chiroptical, nonlinear optical, catalytic and biomedical applications. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
Open AccessReview Coordination Networks Based on Boronate and Benzoxaborolate Ligands
Crystals 2016, 6(5), 48; doi:10.3390/cryst6050048
Received: 29 March 2016 / Revised: 20 April 2016 / Accepted: 27 April 2016 / Published: 2 May 2016
Cited by 1 | PDF Full-text (3990 KB) | HTML Full-text | XML Full-text
Abstract
Despite the extensive range of investigations on boronic acids (R-B(OH)2), some aspects of their reactivity still need to be explored. This is the case for the coordination chemistry of boronate anions (R-B(OH)3), which has only recently been started
[...] Read more.
Despite the extensive range of investigations on boronic acids (R-B(OH)2), some aspects of their reactivity still need to be explored. This is the case for the coordination chemistry of boronate anions (R-B(OH)3), which has only recently been started to be studied. The purpose of this review is to summarize some of the key features of boronate ligands (and of their cyclic derivatives, benzoxaborolates) in materials: (i) coordination properties; (ii) spectroscopic signatures; and (iii) emerging applications. Full article
(This article belongs to the Special Issue Boron-Based (Nano-)Materials: Fundamentals and Applications)
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