Activation Energy For Dehydrogenation Reaction Research Articles

Enhancing hydrogen storage properties of MgH2 using FeCoNiCrMn high entropy alloy catalysts

Herein, we report the successful preparation of the FeCoNiCrMn high entropy alloy (HEA) loaded MgH2 and HEA's effect on the hydrogen storage properties of Mg/MgH2. The HEA shows high catalytic activity toward hydrogen dissociation and recombination reaction, and successfully suppressed activation energy of dehydrogenation reaction from 151.9 to 90.2 kJ mol–1. Moreover, part of Co and Ni can react with Mg, and produce Mg2Co/Mg2CoH5 and Mg2Ni/Mg2NiH4 during the hydrogen storage processes, further enhancing dehydrogenation reaction through the “hydrogen pumping” mechanism. As a result, the MgH2–5 wt% HEA composite can release 5.6 wt% of H2 at 280 °C within 10 min, and absorb 5.5 wt% H2 within 0.5 min at 150 °C. The loaded HEA shows robustness against particle aggregation, leading to stable reversible hydrogen storage processes at least 50 times. These findings show the synergistic effects of HEA on Mg-based hydrogen storage materials, providing an additional degree of freedom for catalyst design.

Enhancing hydrogen storage properties of MgH2 by core-shell CoNi@C

Introducing multicomponent nanoparticles can improve remarkably de/hydrogenation kinetic properties of MgH2. In this work, the original core-shell CoNi@C bimetallic nanoparticles were obtained via hydrothermal and calcination reduction technology. MgH2-8 wt% CoNi@C starts to dehydrogenate at 173 °C with the dehydrogenation capacity of 5.83 wt% within 1800 s at 275 °C. Moreover, the composite absorbs 4.83 wt% H2 within 1800 s at 100 °C with prominent advantage at low temperature. The notable improvement of hydrogen storage properties of MgH2 is attributed to the reversible phase transitions of Mg2Co/Mg2CoH5 and Mg2Ni/Mg2NiH4, and the excellent thermal conductivity and confinement effect of the carbon shell. As a result, the apparent activation energy of dehydrogenation reaction reduces to 78.5 kJ/mol. This work extends the horizon of bimetallic nanoparticles with especial microstructure for enhancing the hydrogen storage properties of metal hydrides.

Characterization of microstructure, hydrogen storage kinetics and thermodynamics of a melt-spun Mg86Y10Ni4 alloy

Ternary Mg86Y10Ni4 alloy was successfully prepared by vacuum induction melting and subsequent melt-spinning technique. The phase composition and microstructure of the melt-spun and hydrogenated samples were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy measurements. The melt-spun alloy had an amorphous structure, and it transformed into nanocrystalline during the first hydrogenation process. The hydrogenated sample was composed of MgH2, Mg2NiH4, YH2, and a small amount of YH3. The hydrogen absorption/desorption kinetics and thermodynamics were measured by Sievert's apparatus at various temperatures. It was found that the melt-spun Mg86Y10Ni4 alloy could be fully activated after five hydrogenation and dehydrogenation cycles at 380 °C, and it exhibited a reversible gravimetric hydrogen storage capacity of about 5.3 wt%. The enhanced hydrogen sorption kinetics during the first few cycles can be attributed to the increased specific surface caused by the pulverization and cracking of the alloy particles. The activation energy for dehydrogenation reaction was determined to be 67 kJ/mol and 71 kJ/mol by using Arrhenius equation and Kissinger equation respectively. The thermodynamics of the sample was also evaluated by pressure–composition–isotherms, and the results shown that the enthalpy and entropy changes of Mg/MgH2 transformation in the Mg86Y10Ni4 alloy were slightly higher than that of pure Mg/MgH2.

Selective doping of nitrogen into carbon materials without catalysts

Selective doping of nitrogen into carbon materials in the absence of catalysts is a key for various applications of carbon materials. It is well known that most nitrogen-containing raw materials generate unnecessary functional groups during carbonization. Many researchers have noticed the significance of the selective nitrogen doping, whereas only a few works have reported the selective doping. In addition, those few works used catalysts to synthesize nitrogen-doped carbon materials, but the presence of catalysts limits the applications of nitrogen-doped carbon materials. This study found an unusual aromatic compound, imidazo[1,2-a]pyridine (IP), which maintained 88 % of the functional groups of as-received IP even after carbonization at 673 K in the absence of catalysts, and the functional groups were further maintained up to 773 K. The percentage of remaining functional groups was revealed using our state-of-the-art techniques of simulated X-ray photoelectron spectroscopy and Raman spectroscopy combined with transition state calculation using density functional theory. The low carbonization temperature as well as selective doping of nitrogen was achieved because of the low activation energy of dehydrogenation reaction among IP molecules compared to the high activation energy of radical formation for scission of C–N bonding.

Studies on the de/re-hydrogenation characteristic of Mg(NH2)2/LiH mixture admixed with carbon nanofibres

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.