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1.
Phys Chem Chem Phys ; 22(1): 368-378, 2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31819933

RESUMO

Metal borohydrides are considered promising materials for hydrogen storage applications due to their high volumetric and gravimetric hydrogen density. Recently, different Lewis bases have been complexed with Mg(BH4)2 in efforts to improve hydrogenation/dehydrogenation properties. Notably, Mg(BH4)2·xTHF adducts involving tetrahydrofuran (THF; C4H8O) have proven to be especially interesting. This work focuses on exploring the physicochemical properties of the THF-rich Mg(BH4)2·3THF adduct using neutron-scattering methods and molecular DFT calculations. Structural analysis, based on neutron diffraction measurements of Mg(11BH4)2·3TDF (D - deuterium), has confirmed a lowering of the symmetry upon cooling, from monoclinic C2/c to P1[combining macron] via a triclinic distortion. Vibrational properties are strongly influenced by the THF environment, showing a splitting in spectral features as a result of changes in the bond lengths, force constants, and lowering of the overall symmetry. Interestingly, the orientational mobilities of the BH4- anions obtained from quasielastic neutron scattering (QENS) are not particularly sensitive to the presence of THF and compare well with the mobilities of BH4- anions in unsolvated Mg(BH4)2. The QENS data point to uniaxial 180° jump reorientations of the BH4- anions around a preferred C2 anion symmetry axis. The THF rings are also found to be orientationally mobile, undergoing 180° reorientational jumps around their C2 molecular symmetry axis with jump frequencies about an order of magnitude lower than those for the BH4- anions. In contrast, no dynamical behavior of the THF rings is observed with QENS for a more THF-deficient 2Mg(BH4)2·THF adduct. This lack of comparable THF mobility may reflect a stronger Mg2+-THF bonding interaction for lower THF/Mg(BH4)2 stoichiometric ratios, which is consistent with DFT calculations showing a decrease in the binding energy with each additional THF ring in the adduct. Based on the combined experimental and computational results, we propose that combining THF and Mg(BH4)2 is beneficial to (i) preventing weakly bound THF from coming free from the Mg2+ cation and reducing the concentration of any unwanted impurity in the hydrogen and (ii) disrupting the stability of the crystalline phase, leading to a lower melting point and enhanced kinetics for any potential hydrogen storage applications.

2.
ACS Appl Mater Interfaces ; 9(18): 15502-15509, 2017 May 10.
Artigo em Inglês | MEDLINE | ID: mdl-28436647

RESUMO

An effective route based on space-confined chemical reaction to synthesize uniform Li2Mg(NH)2 nanoparticles is reported. The hierarchical pores inside the one-dimensional carbon nanofibers (CNFs), induced by the creation of well-dispersed Li3N, serve as intelligent nanoreactors for the reaction of Li3N with Mg-containing precursors, resulting in the formation of uniformly discrete Li2Mg(NH)2 nanoparticles. The nanostructured Li2Mg(NH)2 particles inside the CNFs are capable of complete hydrogenation and dehydrogenation at a temperature as low as 105 °C with the suppression of ammonia release. Furthermore, by virtue of the nanosize effects and space-confinement by the porous carbon scaffold, no degradation was observed after 50 de/rehydrogenation cycles at a temperature as low as 130 °C for the as-prepared Li2Mg(NH)2 nanoparticles, indicating excellent reversibility. Moreover, the theoretical calculations demonstrate that the reduction in particle size could significantly enhance the H2 sorption of Li2Mg(NH)2 by decreasing the relative activation energy barrier, which agrees well with our experimental results. This method could represent an effective, general strategy for synthesizing nanoparticles of complex hydrides with stable reversibility and excellent hydrogen storage performance.

3.
Inorg Chem ; 54(8): 4120-5, 2015 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-25815415

RESUMO

Mg(B3H8)2·2THF (THF = tetrahydrofuran) was prepared by the addition of BH3·THF to Mg/Hg amalgam. Heating a 1:2 molar mixture of Mg(B3H8)2·2THF and MgH2 to 200 °C under 5 MPa H2 for 2 h leads to nearly quantitative conversion to Mg(BH4)2. The differential scanning calorimetry profile of the reaction measured under 5 MPa H2 shows an initial endothermic feature at ∼65 °C for a phase change of the compound followed by a broad exothermic feature that reaches a maximum at 130 °C corresponding to the hydrogenation of Mg(B3H8)2 to Mg(BH4)2. Heating Mg(B3H8)2·2THF to 200 °C under 5 MPa H2 pressure in the absence of MgH2 gives predominantly MgB12H12 as well as significant amounts of MgB10H10 and Mg(BH4)2. Hydrogenation of a mixture of Mg(B3H8)2·2THF and LiH in a 1:4 molar ratio at 130 °C under 5 MPa H2 yields [B12H12](2-) in addition to [BH4](-), while a 1:4 molar ratio of Mg(B3H8)2·2THF and NaH yields [BH4](-) and a new borane, likely [B2H7](-). Hydrogenation of the NaH-containing mixture at 130 °C gives primarily the alternative borane, indicating it is an intermediate in the two-step conversion of the triborane to [BH4](-). The solvent-free triborane Mg(B3H8)2, derived from the low-temperature dehydrogenation of Mg(BH4)2, also produces Mg(BH4)2, but higher temperature and pressure is required to effect the complete transformation of the Mg(B3H8)2. These results show that the reversible transformation of the triborane depends on the stability of the metal hydride. The more stable the metal hydride, that is, LiH > NaH > MgH2, the lower is the "regeneration" efficiency.

4.
Chem Commun (Camb) ; 50(45): 5987-9, 2014 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-24763968

RESUMO

A previously known iridium POCOP pincer catalyst was found to selectively dehydrogenate the heterocyclic portion of several indolic and carbazolic molecules. These molecules were found to have an "activity window" (172-178 °C) upon which only the heterocyclic ring underwent dehydrogenation. All reactions were run solvent free, yields for selected substrates were excellent, and the products were isolated by either distillation or alumina plug filtration.


Assuntos
Carbazóis/síntese química , Indóis/síntese química , Irídio/química , Carbazóis/química , Catálise , Cromatografia Gasosa-Espectrometria de Massas , Indóis/química , Estrutura Molecular
5.
Phys Chem Chem Phys ; 15(17): 6179-81, 2013 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-23519072

RESUMO

The direct synthesis of NaAlH4 has been studied, for the first time, by in situ (27)Al and (23)Na wide-line NMR spectroscopy using high pressure NMR apparatus. Na3AlH6 formation is observed within two minutes of hydrogen addition, while NaAlH4 is detected after a total of four minutes. This indicates the formation of the hexahydride does not proceed to completion before the formation of the tetrahydride ensues.


Assuntos
Compostos de Alumínio/síntese química , Compostos de Sódio/síntese química , Alumínio/química , Compostos de Alumínio/química , Espectroscopia de Ressonância Magnética , Pressão , Sódio/química , Compostos de Sódio/química
6.
J Am Chem Soc ; 133(39): 15593-7, 2011 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-21863886

RESUMO

The direct synthesis of LiAlH(4) from commercially available LiH and Al powders in the presence of TiCl(3) and Me(2)O has been achieved for the first time. The effects of TiCl(3) loadings (Ti/Al = 0, 0.01, 0.05, 0.2, 0.5, 1.0 and 2.0%) and various other additives (TiCl(3)/Al(2)O(3), metallic Ti, Nb(2)O(5), and NbCl(5)) on the formation and stability of LiAlH(4) have been systematically investigated. The yield of LiAlH(4) initially increases, and then decreases, with increasing TiCl(3) loadings. LiH + Al → LiAlH(4) yields above 95% were obtained when the molar ratios of Ti/Al were 0.05 and 0.2%. In the presence of a very tiny amount of TiCl(3) (Ti/Al = 0.01%), LiAlH(4) is still generated, but the yield is lower. In the complete absence of TiCl(3), LiAlH(4) does not form. Addition of metallic Ti, Nb(2)O(5), and NbCl(5) to commercial LiH and Al does not result in the formation of LiAlH(4). Preliminary tests show that TiCl(3)-doped LiAlH(4) can be cycled, making it a suitable candidate for hydrogen storage.

7.
Chem Commun (Camb) ; 47(4): 1330-2, 2011 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-21107458

RESUMO

Thermal decomposition of magnesium borohydride, Mg(BH(4))(2), in the solid state was studied by a combination of PCT, TGA/MS and NMR spectroscopy. Dehydrogenation of Mg(BH(4))(2) at 200 °C en vacuo results in the highly selective formation of magnesium triborane, Mg(B(3)H(8))(2). This process is reversible at 250 °C under 120 atm H(2). Dehydrogenation at higher temperature, >300 °C under a constant argon flow of 1 atm, produces a complex mixture of polyborane species. A borohydride condensation mechanism involving metal hydride formation is proposed.


Assuntos
Boranos/química , Compostos de Magnésio/química , Magnésio/química , Espectroscopia de Ressonância Magnética , Pressão , Temperatura
8.
Faraday Discuss ; 151: 297-305; discussion 385-97, 2011.
Artigo em Inglês | MEDLINE | ID: mdl-22455076

RESUMO

The activity of the PCP pincer complex IrH2{C6H3-2,6-(OPBu(t)2)2)}, (3) as a catalyst for the dehydrogenation of the potential liquid organic hydrogen carriers: perhydro-dibenzofuran (4), perhydro-indole (5), N-methyl perhydro-indole (6), 4,4'-bipiperridine (7), 4-amino-methylpiperridine (8), and aminomethylcyclohexane (9) was investigated. Only low levels of dehydrogenation were achieved with 4 at 150 and 200 degrees C except in the presence a hydrogen acceptor, 3,3-dimethyl-1-butene (tbe). At temperatures above 150 degrees C, 3 showed high activity with 5 but only for the release of H2 across the C-N bond. Dehydrogenation of 6 at 150 degrees C was found to release up to 2.9 wt% H2, giving N-methyl tetrahydroindole in 92% yield, but only 7% N-methyl indole. However, efficient dehydrogenation of the aliphatic hydrogens occurred at 200 degrees C giving mixtures that approached a approximately 1:3 equilibrium between N-methyl indole and N-methyl tetrahydroindole at longer reaction times. The pincer catalyst was observed to be effective for the dehydrogenation of 7 and 8 at 200 degrees C but the products polymerize. The catalytic dehydrogenation of 9 was very efficient at 200 degrees C but gave primarily the undesired products dibenzylamine (68%), benzylidenebenzylamine (22%), ammonia and only minor amount of benzonitrile (10%). At 160 degrees C, 85% of the substrate was consumed after 24 h of heating but only a minor amount of cyclohexanecarbonitrile (2%) was detected with the major products being biscyclohexylmethylamine (45%) and cyclohexylmethyl-cyclohexylimine (38%). The nitrile yield is remarkably improved to 97% when the dehydrogenation was carried out at 160 degrees C in the presence of 10 mol% NaOBu(t) but heating the reaction mixtures containing the base to 200 degrees C resulted in the decomposition of the pincer catalyst.

9.
Chem Commun (Camb) ; 46(3): 421-3, 2010 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-20066312

RESUMO

Conditions have been found whereby it is possible to reversibly store >11 wt% hydrogen through the direct hydrogenation of MgB(2) to Mg(BH(4))(2).

10.
Nanotechnology ; 20(20): 204027, 2009 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-19420675

RESUMO

A new approach to the incorporation of MgH2 in the nanometer-sized pores of a carbon aerogel scaffold was developed, by infiltrating the aerogel with a solution of dibutylmagnesium (MgBu2) precursor, and then hydrogenating the incorporated MgBu2 to MgH2. The resulting impregnated material showed broad x-ray diffraction peaks of MgH2. The incorporated MgH2 was not visible using a transmission electron microscope, which indicated that the incorporated hydride was nanosized and confined in the nanoporous structure of the aerogel. The loading of MgH2 was determined as 15-17 wt%, of which 75% is reversible over ten cycles. Incorporated MgH2 had >5 times faster dehydrogenation kinetics than ball-milled activated MgH2, which may be attributed to the particle size of the former being smaller than that of the latter. Cycling tests of the incorporated MgH(2) showed that the dehydrogenation kinetics are unchanged over four cycles. Our results demonstrate that confinement of metal hydride materials in a nanoporous scaffold is an efficient way to avoid aggregation and improve cycling kinetics for hydrogen storage materials.


Assuntos
Carbono/química , Cristalização/métodos , Hidrogênio/química , Hidrogênio/isolamento & purificação , Magnésio/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Ar , Gases/química , Géis/química , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Nanotecnologia/métodos , Tamanho da Partícula , Propriedades de Superfície
11.
J Am Chem Soc ; 131(14): 5032-3, 2009 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-19296609

RESUMO

LiH and Ti-doped Al react quantitatively with H(2) in Me(2)O solution to form LiAlH(4) under mild conditions. The solvent is easily vented along with excess H(2) on completion, leaving dry Ti-doped LiAlH(4); this releases approximately 7 wt % H(2) commencing at 80 degrees C with excellent kinetics.

12.
J Phys Chem A ; 112(33): 7551-5, 2008 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-18665574

RESUMO

LiSc(BH4)4 has been prepared by ball milling of LiBH4 and ScCl3. Vibrational spectroscopy indicates the presence of discrete Sc(BH4)4(-) ions. DFT calculations of this isolated complex ion confirm that it is a stable complex, and the calculated vibrational spectra agree well with the experimental ones. The four BH4(-) groups are oriented with a tilted plane of three hydrogen atoms directed to the central Sc ion, resulting in a global 8 + 4 coordination. The crystal structure obtained by high-resolution synchrotron powder diffraction reveals a tetragonal unit cell with a = 6.076 A and c = 12.034 A (space group P-42c). The local structure of the Sc(BH4)4(-) complex is refined as a distorted form of the theoretical structure. The Li ions are found to be disordered along the z axis.

13.
Chem Rev ; 107(10): 4111-32, 2007 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-17848101
14.
J Phys Chem B ; 110(18): 9105-11, 2006 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-16671722

RESUMO

A systematic study of the dehydrogenation process of undoped and of catalyzed NaAlH4 by means of anelastic spectroscopy is presented. Evidence is reported of the formation of a highly mobile species during decomposition, which has been identified in off-stoichiometric AlH6-x units, giving rise to fast H vacancy local dynamics. The formation of such stoichiometry defects starts at temperatures much lower in Ti doped than in undoped samples, and concomitantly with the decomposition reaction. The catalyst atoms decrease the energy barrier to be overcome by H to break the bond, thus enhancing the kinetics of the chemical reactions and decreasing the temperature at which the dehydrogenation processes take place. The experimental data show that not all the hydrogen released by the formula units during the evolution of decomposition evolves out of the sample, but part of it remains in the lattice and migrates on a long-range scale within the sample. We identify, in this H mobilized population, the species which induces the fast tetragonal to monoclinic phase transformation accompanying decomposition. A partial spontaneous thermally activated regression of decomposition has also been observed by aging experiments. A model is proposed which accounts for the action of the Ti catalyst and for the atomistic mechanism of decomposition.

15.
J Phys Chem B ; 110(6): 2740-5, 2006 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-16471879

RESUMO

NaAlH(4) with TiCl(3) and Al were mixed by ball-milling and cycled three times. The hydrogen storage properties were monitored during cycling, and the products were characterized by synchrotron X-ray diffraction. Because of the previously described formation of Al(1)(-)(y)Ti(y) with y approximately 0.15 during cycling that traps Al beyond the amount associated with the formation of NaCl, some Na(3)AlH(6) has no free Al to react with to form NaAlH(4). This was counteracted in the present work by adding a stoichiometric amount of Al that increases the theoretical storage capacity. Due to limitations in metal diffusion small amounts of Na(3)AlH(6) were still detected. When approximately 7 mol % more Al than the stoichiometric amount was added, the observed storage capacity increased significantly, and the Na(3)AlH(6) content was negligible after prolonged rehydrogenation. Cycled NaAlH(4) + 10 mol % TiCl(3) were desorbed to two different levels, and the diffraction patterns were compared. There is no change in unit-cell dimensions during desorption, and there is no sign of changes in the bulk composition of the Al(1)(-)(y)Ti(y) phase during a cycle. Adding pure Ti to a NaH + Al mixture by ball-milling in argon or hydrogen results in formation of TiH(2) that is stable during at least one cycle.

16.
J Phys Chem B ; 109(3): 1168-73, 2005 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-16851077

RESUMO

We report the first measurements of elastic modulus and energy dissipation in Ti-doped and undoped sodium aluminum hydride. It is shown that the chemical reactions that occur by varying the sample temperatures or by aging most sensitively affect the elastic constants, such that the modulus variations allow the time and temperature evolution of decomposition to be monitored. After a well-defined thermal treatment at 436 K, a thermally activated relaxation process appears at 70 K in the kilohertz range, denoting the existence of a new species, likely involving hydrogen, having a very high mobility, that is, 10(3) jumps/s at the peak temperature corresponding to a relaxation rate of about 10(11) s(-1) at room temperature. The activation energy of the process is 0.126 eV and the preexponential factor 7 x 10(-14) s, which is typical of point defect relaxation. The peak is very broad with respect to a single Debye process, indicating strong interaction or/and multiple jumping type of the mobile entity. The present data suggest that the models aiming at interpreting the decomposition reactions and kinetics should take into account the indicated point-defect dynamics and stoichiometry defects.

17.
J Phys Chem B ; 109(33): 15780-5, 2005 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-16853003

RESUMO

NaAlH4 samples with Ti additives (TiCl3, TiF3, and Ti(OBu)4) have been investigated by synchrotron X-ray diffraction in order to unveil the nature of Ti. No crystalline Ti-containing phases were observed after ball milling of NaAlH4 with the additives, neither as a solid solution in NaAlH4 nor as secondary phases. However, after cycling, a high-angle shoulder of Al is observed in the same position with 10% TiCl3 as that with 2% Ti(OBu)4, but with considerably higher intensity, indicating that the shoulder is caused by Ti. After prolonged reabsorption, there is only a small fraction of free Al phase left to react with Na3AlH6, whereas the shoulder caused by Al(1-y)Ti(y) is dominating. The Ti-containing phase causing the shoulder therefore contains less Ti than Al3Ti, and the aluminum in this phase is too strongly bound to react with Na3AlH6 to form NaAlH4. The composition of the Al(1-y)Ti(y) phase is estimated from quantitative phase analysis of powder X-ray diffraction data to be Al(0.85)Ti(0.15). Formation of this phase may explain the reduction of capacity beyond the theoretical reduction from the dead weight of the additive and the reaction between the additive and NaAlH4.

18.
Chem Commun (Camb) ; (8): 818-9, 2002 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-12122995

RESUMO

[PdCl(C6H3(OPPri2)2-2,6)] 1 catalyses the coupling of electron-rich, electron-neutral and electron-deficient aryl chlorides with phenylacetylene in the presence of ZnCl2 as cocatalyst to give the products in modest to excellent yields.


Assuntos
Acetileno/análogos & derivados , Acetileno/metabolismo , Cloretos/farmacologia , Hidrocarbonetos Aromáticos/síntese química , Hidrocarbonetos Clorados/síntese química , Paládio/farmacologia , Compostos de Zinco/farmacologia , Acetileno/química , Catálise , Relação Estrutura-Atividade
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