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The present investigation deals with the synthesis of ternary transition metal alloy nanoparticles of FeCoNi and graphene templated FeCoNi (FeCoNi@GS) by one-pot reflux method and there use as a catalyst for hydrogen sorption in MgH2. It has been found that the MgH2 catalyzed by FeCoNi@GS (MgH2: FeCoNi@GS) has the onset desorption temperature of ~255 °C which is 25 °C and 100 °C lower than MgH2 catalyzed by FeCoNi (MgH2: FeCoNi) (onset desorption temperature 280 °C) and the ball-milled (B.M) MgH2 (onset desorption temperature 355 °C) respectively. Also MgH2: FeCoNi@GS shows enhanced kinetics by absorbing 6.01 wt% within just 1.65 min at 290 °C under 15 atm of hydrogen pressure. This is much-improved sorption as compared to MgH2: FeCoNi and B.M MgH2 for which hydrogen absorption is 4.41 wt% and 1.45 wt% respectively, under the similar condition of temperature, pressure and time. More importantly, the formation enthalpy of MgH2: FeCoNi@GS is 58.86 kJ/mol which is 19.26 kJ/mol lower than B.M: MgH2 (78.12 kJ/mol). Excellent cyclic stability has also been found for MgH2: FeCoNi@GS even up to 24 cycles where it shows only negligible change from 6.26 wt% to 6.24 wt%. A feasible catalytic mechanism of FeCoNi@GS on MgH2 has been put forward based on X-ray diffraction (XRD), Raman spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Photoelectron Spectroscopy (XPS), and microstructural (electron microscopic) studies.

We describe the synthesis of MgH2 using autocatalytic effect of MgH2. The MgH2 was synthesized by ball milling Mg with 5 wt% of MgH2. The ball milling was carried out at different pressures of 15, 30 and 45 atm of H2 followed by heat treatment (heating under vacuum and annealing at 30 atm of H2 pressure (at 350 °C) for 10 h). It has been found that the MgH2 synthesized using 30 atm of H2 pressure during ball milling, followed by heat treatment and annealing (MgH230BM) is the optimum material as it has lowest desorption temperature (325 °C) faster rehydrogenation kinetic (6.60 wt% within 30 min at 300 °C and 20 atm hydrogen pressure). Also MgH230BM maintains the storage capacity of more than 6.00 wt% (loss of 0.6 wt%) after 10 cycles of de/re-hydrogenation. The as synthesized MgH2 has superior de/re-hydrogenation properties and is ∼4 times cheaper as compared to MgH2 procured from the chemical company like Alfa-Aesar. It is to be mentioned that under above mentioned temperature and pressure conditions the stand alone Mg (without having MgH2 as catalyst) doesnot at all converts to MgH2. The present study opens the gateway for economical synthesis of MgH2 at large scale.

The present study deals with the material tailoring of Mg(NH2)2–2LiH through dual borohydrides: the reactive LiBH4 and the non-reactive NaBH4. Furthermore, a pulverizer, as well as a catalyst FeTi, has been added in order to facilitate hydrogen sorption. Addition of LiBH4 to LiNH2 in a 1 : 3 molar ratio leads to the formation of Li4(BH4)(NH2)3 which also acts as a catalyst. However, the addition of NaBH4 doesn't lead to any compound formation but shows a catalytic effect. The onset dehydrogenation temperature of thermally treated Mg(NH2)2–2LiH/(Li4(BH4)(NH2)3–NaBH4) is 142 °C as against 196 °C for the basic material Mg(NH2)2–2LiH. However, with the FeTi catalyzed Mg(NH2)2–2LiH/(Li4(BH4)(NH2)3–NaBH4, it has been reduced to 120 °C. This is better than other similar amide/hydride composites where it is 149 °C (when the basic material is catalyzed with LiBH4). The FeTi catalyzed Mg(NH2)2–2LiH/(Li4(BH4)(NH2)3–NaBH4 sample shows better de/re-hydrogenation kinetics as it desorbs 3.9 ± 0.04 wt% and absorbs nearly 4.1 ± 0.04 wt% both within 30 min at 170 °C (with the H2 pressure being 0.1 MPa for desorption and 7 MPa for absorption). The eventual hydrogen storage capacity of Mg(NH2)2–2LiH/(Li4(BH4)(NH2)3–NaBH4 together with FeTi has been found to be ∼5.0 wt%. To make the effect of catalysts intelligible, we have put forward in a schematic way the role of Li and Na borohydrides with FeTi for improving the hydrogen sorption properties of Mg(NH2)2–2LiH.

The present study reports the curious catalytic action of a new class of catalyst, quasicrystal of Al65Cu20Fe15 on de/rehydrogenation properties of magnesium hydride (MgH2). Catalyzed through this catalyst, the onset desorption temperature of MgH2 gets reduced significantly from ∼345 °C (for ball-milled MgH2) to ∼215 °C. A more dramatic effect of the above catalyst has been observed on rehydrogenation. Here, 6.00 wt % of hydrogen storage capacity is observed in just 30 s at 250 °C. Improved rehydrogenation kinetics has been found even at lower temperatures of 200 and 150 °C by absorbing ∼5.50 and ∼5.40 wt % of H2, respectively, within 1 min and ∼5.00 wt % at 100 °C in 30 min. These are some of the lowest desorption temperatures and rehydrogenation kinetics obtained for MgH2 through any other known catalyst. The storage capacity of MgH2 catalyzed with the leached version of Al65Cu20Fe15 quasicrystalline alloy degrades negligibly even after 51 cycles of de/rehydrogenation. The feasible reason for catalytic ...

The present investigation describes the synergistic role of Li4(BH4)(NH2)3 and ZrFe2 in the hydrogen storage behaviour of a Li–Mg–N–H hydride system. The onset desorption temperature of ZrFe2-catalysed Mg(NH2)2–LiH–Li4(BH4)(NH2)3 is ∼122 °C, which is 83 °C, 63 °C, and 28 °C lower than that of thermally treated 2LiNH2–1MgH2, 2LiNH2–1MgH2–4 wt%ZrFe2, and 2LiNH2–1MgH2–0.1LiBH4 composites, respectively. Native Mg(NH2)2–LiH–Li4(BH4)(NH2)3 absorbed only 2.78 wt% of H2 within 30 min. On the other hand, the ZrFe2-catalysed Mg(NH2)2–LiH–Li4(BH4)(NH2)3 sample absorbed 3.70 wt% of hydrogen within 30 min and 5 wt% of H2 in 6 h at 180 °C and 7 MPa H2 pressure. Mg(NH2)2–LiH–Li4(BH4)(NH2)3 catalyzed with ZrFe2 shows negligible degradation of the storage capacity even after repeated cycles of de/rehydrogenation. The effect of ZrFe2 and Li4(BH4)(NH2)3 on a Mg(NH2)2/LiH composite has been described and discussed with the help of structural (X-ray diffraction), microstructural (electron microscopy), and vibrational modes of molecules through FTIR studies. The present results suggest that an optimum catalysis may originate from the synergistic action of an in situ formed quaternary hydride (Li4(BH4)(NH2)3) and an intermetallic-like ZrFe2, which acts as a pulverizer cum catalyst.

In present investigation, the selective removal of Al from the quasi-lattice sites of quasicrystalline alloy surface was examined in order to produce the nano-particles of metal/metal oxides within the micro-porous network. Al was selectively etched from both the as-cast as well as annealed Al63Cu25Fe12 quasicrystalline alloys through the treatment with 10 mol NaOH solution at different time interval. In the as-cast sample, higher density of porosity was observed compared to that of annealed alloy. However, dealloying specifically for 4 and 8 h yielded nano-size particles on quasicrystalline surface (of both the alloys) in which very fine particles were detected at 8 h. The increase in density and decrease in size of the nano-particles was found with dealloying duration. X-ray diffraction analysis was performed to characterize the samples. Scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analysis were carried out to investigate the surface microstructure, internal morphology and chemical composition. The chemical dealloying treatments yielded nano-particles of Cu and Fe along with their oxides on the quasicrystalline surface. Furthermore, the catalytic activity of leached quasicrystalline materials was evaluated towards degradation of non-biodegradable and hazardous methylene blue (organic dye).

The present communication deals with the hydrogen storage performance of ambient pressure dried pristine as well as platinum doped carbon aerogel (CA-0.10 Pt). These carbon aerogels (CAs) have been prepared from resorcinol-formaldehyde (R–F) through sol–gel synthesis route with sodium carbonate as a catalyst (C). The synthesis parameters adapted led to the formation of CA having preponderance of submicropores. Structural and microstructural characteristics of these carbon aerogels have been investigated through XRD, SEM, TEM, nitrogen adsorption and Raman spectroscopic techniques. Nitrogen adsorption and TEM studies confirm the large density of micropores with the majority of pores having sizes between 0.30 and 1.46 nm (submicropores). The hydrogen storage characteristics of as synthesized carbon aerogels have been investigated by monitoring the hydrogen ad/desorption curves. At room temperature and at pressure upto 22 atm the CA and CA-0.1 Pt have hydrogen storage capacity of 0.40 wt.% and 0.33 wt.% respectively. However, under the same pressure but at liquid nitrogen temperature CA and CA-0.10 Pt have hydrogen storage capacity of 5.65 wt.% and 5.15 wt.%. Feasible reasons for the high hydrogen storage capacities at liquid nitrogen temperature for the present CAs have been put forward.

The present investigation describes the hydrogen sorption (de/absorption) behavior of MgH2 catalyzed by graphene sheet templated Fe3O4 nanoparticles (Fe3O4@GS). Hydrogen sorption studies reveal that MgH2 catalyzed by Fe3O4@GS (MgH2:Fe3O4@GS) offers improved hydrogen storage behavior as compared to stand-alone MgH2 catalyzed by graphene sheets (GS) (MgH2:GS) or Fe3O4 nanoparticles (MgH2:Fe3O4). The MgH2:Fe3O4@GS has an onset desorption temperature of ∼262 °C (∼142 °C lower than pristine MgH2), while MgH2:GS and MgH2:Fe3O4 have onset desorption temperatures of ∼275 °C and ∼298 °C respectively. In contrast to this, MgH2:GS absorbs 4.40 wt% and MgH2:Fe3O4 absorbs 5.50 wt% in 2.50 minutes at 290 °C under 15 atm hydrogen pressure. On the other hand, MgH2:Fe3O4@GS absorbs 6.20 wt% hydrogen in 2.50 minutes (which is considerably higher than recently studied catalyzed MgH2 systems) under identical temperature and pressure conditions. The MgH2 catalyzed with Fe3O4@GS shows negligible degradation of the storage capacity even after 25 cycles. Additionally, the desorption activation energy for MgH2:Fe3O4@GS has been found to be 90.53 kJ mol−1 (which is considerably lower as compared to metal/metal oxide catalyzed MgH2 and fluorographene catalyzed MgH2). The formation enthalpy for MgH2:Fe3O4@GS is 60.62 kJ per mole of H2 (13.44 kJ mol−1 lower than bulk MgH2). The catalytic effect of Fe3O4@GS has been described and discussed with the help of structural (X-ray diffraction (XRD)), micro structural (electron microscopy) and Raman spectroscopic studies.

The present study deals with the use of ZrFe2 for the formation of pure phase of hydrogen storage material Mg(NH2)2/LiH. Since ZrFe2 is harder than the starting material LiNH2 and MgH2, pulverization effect produced by ZrFe2 assists in the synthesis of pure phase. The formation of pure Mg(NH2)2/LiH has been examined by XRD and confirmed by FTIR. The catalytic effect of ZrFe2 has been found to improve significantly the de/rehydrogenation characteristic of Mg(NH2)2/LiH. The ZrFe2 catalyzed Mg(NH2)2/LiH shows good recyclability. The activation energy of ZrFe2 catalyzed Mg(NH2)2/LiH was found to be 74.80 kJ/mol which is better than several other reported studies using different catalysts. Based on experimental results, a viable mechanism for dehydrogenation of Mg(NH2)2 in the presence of ZrFe2 has also been proposed.

The unfavorable de/re-hydrogenation aspects of high storage capacity material, Mg can be overcome by synthesis of composites with known intermetallic hydrogen storage alloys. In this work, a new additive, ZrFe2Hx intermetallic hydride, is used to synthesize MgH2–ZrFe2Hx nanocomposite by reactive mechanical milling technique. Also this report describes the comparison of hydrogen sorption behavior of MgH2–ZrFe2 and MgH2–ZrFe2Hx nanocomposites. It is found that the composite containing ZrFe2 and ZrFe2Hx leads to decrease in desorption temperature from 410 °C (for MgH2) to 350 and 290 °C respectively. The activation energy for rehydrogenation of composite is found to be ∼61 kJ/mol. This is lowered by 30 kJ/mol compared to the pristine milled MgH2 (92 kJ/mol). Thus, the results show significant improvement of hydrogenation behavior with the addition of ZrFe2Hx. Reasons for better catalytic activity achieved by using ZrFe2Hx have been put forwarded. Based on the present studies it can be suggest that the use of hydride version instead of the parent intermetallic phase for synthesizing the composite with MgH2 has a distinct advantage in improving the hydrogenation behavior of MgH2.

The present investigation describes the hydrogen storage properties of 2:1 molar ratio of MgH 2 –NaAlH 4 composite. De/rehydrogenation study reveals that MgH 2 –NaAlH 4 composite offers beneficial hydrogen storage characteristics as compared to pristine NaAlH 4 and MgH 2 . To investigate the effect of carbon nanostructures (CNS) on the de/rehydrogenation behavior of MgH 2 –NaAlH 4 composite, we have employed 2 wt.% CNS namely, single wall carbon nanotubes (SWCNT) and graphene nano sheets (GNS). It is found that the hydrogen storage behavior of composite gets improved by the addition of 2 wt.% CNS. In particular, catalytic effect of GNS + SWCNT improves the hydrogen storage behavior and cyclability of the composite. De/rehydrogenation experiments performed up to six cycles show loss of 1.50 wt.% and 0.84 wt.% hydrogen capacity in MgH 2 –NaAlH 4 catalyzed with 2 wt.% SWCNT and 2 wt.% GNS respectively. On the other hand, the loss of hydrogen capacity after six rehydrogenation cycles in GNS + SWCNT (1.5 + 0.5) wt.% catalyzed MgH 2 –NaAlH 4 is diminished to 0.45 wt.%.

The aim of the present investigation is to synthesize mixed sodium potassium alanate (K2NaAlH6) and to explore its hydrogen sorption characteristics. K2NaAlH6 is synthesized through ball milling of KH and NaAlH4 in the molar ratio 2:1 under hydrogen pressure of 10 bar. The temperature programmed desorption experiment shows that the synthesized K2NaAlH6 has peak desorption temperature of ∼352°C and reveals appreciable rehydrogenation kinetics under 6 bar hydrogen pressure at 300°C. The investigations are also focused on the catalytic effect of carbon nanostructures (CNS) namely, the graphene sheet (GS) and single wall carbon nanotube (SWCNT) and titanium halides (TiCl3 and TiF3) on K2NaAlH6. In the case of graphene and SWCNT catalyzed K2NaAlH6, the peak desorption temperature gets reduced to ∼347°C and ∼341°C respectively. The catalytic effects of CNS and titanium halide on K2NaAlH6 are also compared in the investigation. Between the two types of catalysts, halides are found to be better than CNS and out of the two halides, TiF3 is found to be the best catalyst for hydrogen sorption in K2NaAlH6. The peak desorption temperature decreases significantly from 352°C to ∼324°C for TiF3 catalyzed K2NaAlH6. Thus, the desorption activation energy reduces drastically from 124.43 kJ/mol (synthesized K2NaAlH6) to 88.05 kJ/mol for TiF3 catalyzed K2NaAlH6.

The effect of different carbon nanostructures specifically carbon nanotubes (CNTs) and carbon nanofibers (CNFs) on the improvement of the de/re-hydrogenation characteristics of a Mg(NH2)2/LiH mixture have been studied. Amongst CNTs and CNFs, the improvement in the hydrogenation properties for the Mg(NH2)2/LiH mixture is higher when CNFs are used as a catalyst. Investigations are also focused on the deployment of two different types of CNF (a) CNF1 (synthesized using a ZrFe2 catalyst) and (b) CNF2 (synthesized using a LaNi5 catalyst). The results show that CNF2 is better. The maximum decomposition temperature for the pristine Mg(NH2)2/LiH mixture is found to be ∼250 °C, which is reduced to ∼180 and ∼150 °C for the sample mixed with 4 wt% of multi-walled carbon nanotubes (MWCNTs) and CNF2 respectively. The activation energy for the dehydrogenation reaction is found to be 74 and 68 kJ mol−1 for the samples mixed with MWCNT and CNF2 respectively, whereas the activation energy for the dehydrogenation reaction of the pristine Mg(NH2)2/LiH mixture is 97 kJ mol−1. The catalytic activity and the de/re-hydrogenation characteristics of the Mg(NH2)2/LiH mixture mixed with different carbon nanostructures are described and discussed.

In the present study, we have investigated the combined effect of different transition metals such as Ti, Fe and Ni on the de/rehydrogenation characteristics of nano MgH 2 . Mechanical milling of MgH 2 with 5 wt% each of Ti, Fe and Ni for 24 h at 12 atm of H 2 pressure lead to the formation of nano MgH 2 -Ti5Fe5Ni5. The decomposition temperature of nano MgH 2 -Ti5Fe5Ni5 is lowered by 90 °C as compared to nano MgH 2 alone. It is also found that the nano MgH 2 -Ti5Fe5Ni5 absorbs 5.3 wt% within 15 min at 270 °C and 12 atm hydrogen pressures. However, nano MgH 2 reabsorbs only 4.2 wt% under identical condition. An interesting result of the present study is that mechanical milling of MgH 2 separately with Fe and Ni besides refinement in particle size also leads to the formation of alloys Mg 2 NiH 4 and Mg 2 FeH 6 respectively. On the other hand, when MgH 2 is mechanically milled together with Ti, Fe and Ni, the dominant result is the formation of nano particles of MgH 2 . Moreover the activation energy for dehydrogenation of nano MgH 2 co-catalyzed with Ti, Fe and Ni is 45.67 kJ/mol which is 35.71 kJ/mol lower as compared to activation energy of nano MgH 2 (81.34 kJ/mol). These results are one of the most significant in regard to improvement in de/rehydrogenation characteristics of known MgH 2 catalyzed through transition metal elements.

In the present investigation, we have synthesized different morphologies of carbon nanofibres (CNFs) to investigate their catalytic effect on the hydrogenation characteristics of 25 h ball-milled MgH2 (nano MgH2). The TEM analysis reveals that 25 h of ball-milling leads to the formation of nanocrystalline particles with size ranging between 10 and 20 nm. Different morphologies of CNFs were synthesized by catalytic thermal decomposition of acetylene (C2H2) gas over LaNi5 alloy. Helical carbon nanofibers (HCNFs) were formed at a temperature 650 °C. By increasing the synthesis temperature to 750 °C, planar carbon nanofibres were formed. In order to explore the effectiveness of CNFs towards lowering the decomposition temperature, TPD experiments (at heating rate 5 °C/min) were performed for nano MgH2 with and without CNFs. It was found that the decomposition temperature is reduced to ~334 and ~300 °C from 367 °C for the PCNF and HCNF catalysed nano MgH2. It is also found that HCNF admixed nano MgH2 absorbs ~5.25 wt% within 10 min as compared with pristine nano MgH2, which absorbs only ~4.2 % within the same time and same condition of temperature and pressure. Thus the HCNF possesses better catalytic activity than PCNF. These different levels of improvement in hydrogenation properties of HCNF catalysed nano MgH2 is attributed to the morphology of the CNFs.

The effect of carbon nanofibres (CNFs) on the de/re-hydrogenation characteristics of 1:2 magnesium amide (Mg(NH2)2) and lithium hydride (LiH) mixture is investigated. It is found that the desorption as well as absorption characteristic of the 1:2 Mg(NH2)2/LiH mixture is improved with admixing of different shaped (planar and helical) CNFs separately. The different shaped CNFs were synthesized through catalytic decomposition of acetylene gas over LaNi5 alloy. The synthesized CNFs contain Ni-metal nano particles. Among two different types of nanofibres namely planar carbon nanofibres (PCNFs) and helical carbon nanofibres (HCNFs), the later was found to act as a better catalyst. The decomposition temperature of the pristine Mg(NH2)2/LiH mixture is ∼250 °C, reduced to 150 and 140 °C for the PCNF and HCNF admixed Mg(NH2)2/LiH mixture respectively. The activation energy for dehydrogenation reaction was found to ∼97.2 kJ/mol, which is further reduced to ∼67 and ∼65 kJ/mol for the PCNF and HCNF admixed Mg(NH2)2/LiH mixture respectively. The lowering of decomposition temperature and enhancement in desorption kinetics, with admixing of different shaped CNFs are described and discussed.

In the present study, we have investigated the effect of vanadium and its compounds (V, V 2 O 5 and VCl 3 ) on desorption characteristics of 1:2 magnesium amide (Mg(NH 2 ) 2 ) and lithium hydride (LiH) mixture. The hydrogen storage characteristics of 1:2 Mg(NH 2 ) 2 /LiH mixture gets enhanced with admixing of V, V 2 O 5 and VCl 3 separately. The VCl 3 has been found to be the most effective followed by V and V 2 O 5 . The activation energy for dehydrogenation process of 1:2 Mg(NH 2 ) 2 /LiH mixture with and without catalyst has been evaluated using a method suggested by Ozawa et al. [25] . Based on the experimental results, schematic reaction scheme for decomposition of Mg(NH 2 ) 2 in the presence of VCl 3 has also been proposed.

This paper reports mischmetal (Mm) as an effective catalyst for fast desorption kinetics (3.7 wt% in 60 min in which ∼3.3 wt% observed in 30 min and ∼5 wt% in 180 min at the desorption temperature of 150 °C for the 2 mol% Mm-doped material) and rehydrogenation (up to 35 cycles) of the light weight hydrogen storage material NaAlH 4 . In fact this catalyst Mm has been shown to be better than the presently known catalyst Ti. For Mm, its presence when admixed in NaAlH 4 is discernible. Also the higher reversible hydrogen storage capacity (4.77 wt% which is 86% of the total reversible storage capacity) of the total is achievable in the 12th cycle. The possible modes of catalyst Mm for fast desorption kinetics has been outlined and the most feasible mechanism in terms of weakening of Na and AlH 4 bonding has been put forward.