Improvement in hydrogen storage performance of Mg by mechanical grinding with molten salt etching Ti3C2Clx

Mg-based materials are currently a hot research topic as hydrogen storage materials due to their considerable theoretical hydrogen storage capacity. However, the kinetic performance of hydrogen absorption and desorption of Mg is too slow and requires high temperature, which seriously hinders the application of this material. MXene is a new type of two-dimensional material with significant role in improving thermodynamics and kinetics. In this experiment, a two-dimensional layered MXene containing Cl functional group was prepared by molten salt etching using the Ti-containing MAX phase as the raw material. Then different ratios of Ti₃C₂Cl_x were uniformly dispersed onto the surface of Mg by high energy ball milling. The samples were characterized by hydrogen absorption and desorption kinetics, SEM, XRD, XPS, and DSC to investigate the effect of Ti₃C₂Cl_x on the hydrogen absorption and desorption performance of Mg. The onset hydrogen absorption temperature can be reduced to room temperature and the hydrogen release temperature is reduced by 200 ​°C by doping Ti₃C₂Cl_x. And there is also 5.4 ​wt% hydrogen storage in the isothermal hydrogen absorption test at 400 ​°C. The results of DSC demonstrate that the E_a of Mg+15 ​wt% Ti₃C₂Cl_x was reduced by 12.6% compared to pristine Mg. The ΔH is almost invariable. The results of XPS show that the presence of multivalent Ti promotes electron transfer and thus improves the conversion between Mg²⁺/Mg and H⁻/H. This study provides a guideline for further improving the hydrogen absorption and desorption performance of Mg-based hydrogen storage materials.     

贮氢合金的开发与研究进展

贮氢合金是近年来开发的一类新型高性能材料。本文介绍了贮氢合金的开发和研究的最新进展,论述了它在氢的提纯、热泵、空调、压缩机和镍—氢化物电池等高技术领域中的应用前景。     

Co~（2＋）、Ni~（2＋）、Cd~（2＋）对过氧化氢酶动力学的影响

在生理条件下，本实验探索了Ｃｏ２＋、Ｎｉ２＋、Ｃｄ２＋对过氧化氢稳定性和过氧化氢酶生物活性的影响。结果表明，Ｃｏ２＋、Ｎｉ２＋、Ｃｄ２＋对过氧化氢的分解反应具有正催化作用，对过氧化氢酶的生物活性均有可逆的抑制作用，其抑制能力的大小顺序为Ｃｏ２＋＞Ｃ２＋＞Ｎｉ２＋。     

邻二氮杂苯-水复合物氢键结构的理论研究

用直接密度泛函理论B3LYP方法对邻二氮杂苯-水复合物基态的氢键结构与相互作用能进行了理论计算，结果表明复合物之间存在较强的氢键N…H—O相互作用，在复合物中，水的H—O对称伸缩振动频率明显红移，计算结果与实验值吻合较好．     

CNa42+团簇的结构及其储氢性能研究

氢是一种理想的二次能源,它将成为化石燃料最有希望的替代能源之一,也是亟待开发的重要能源。而氢能的储存成本高,危险性大是急需解决的问题。理论上预测CNa_4~(2+)的储氢性能,通过理论分析,发现了每个CNa_4~(2+)团簇最多可与16个H2分子有效结合,获得23.5%的质量储氢密度。在B3LYP理论水平上,H2分子与CNa_4~(2+)团簇的平均相互作用能在2.107～4.948Kcal/mol之间。由于CNa_4~(2+)的质量储氢密度在7.1～23.7wt%之间,符合美国能源部的要求目标(5.5 wt%)。研究结果表明,CNa_4~(2+)在一定环境条件下可逆吸放氢性能良好,可作为潜在的理想高容量储氢材料。     

Microstructure characterization and hydrogen storage properties study of Mg2Ni0.92M0.08 (M = Ti, V, Fe or Si) alloys

In the present study Mg_2Ni-type compounds alloyed independently with Ti,V,Fe and Si were successfully prepared by wet-milling followed by sintering.Although these alloyed Mg_2Ni compounds exhibited a similar hydrogen storage mechanism as that of pure Mg_2Ni,the dissolution of Ti,V or Fe into the Mg_2NiH_4lattice had a considerable catalytic effect on hydrogen desorption from additional MgH_2.The further structure investigations clearly indicated that the substitution of Ti for Ni could suppress the formation of the micro-twined low-temperature phase(LT2)and promote the formation of the high-temperature phase(HT),thus resulting in remarkably improved hydrogen desorption kinetics for the Mg_2Ni_(0.92)Ti_(0.08)–H system.     

Experimental investigation and thermodynamic assessment of the yttriumhydrogen binary system

A coupled experimental investigation and thermodynamic study of the yttrium-hydrogen(Y-H) binary system were carried out to provide more comprehensive and quantitative insights into the key thermodynamic properties of this system. Y-H system in the full range of H/Y = 0–3.0 was investigated by accurate pressure composition isotherm(PCI) measurement to provide credible phase equilibria information and thermodynamic data.The phase boundaries obtained were in agreement with previous experimental data but with improved accuracy.With the guide of the crystal structures, all the solid phases were modelled using the three sublattice model. The Y-H phase diagram and thermodynamic parameters were calculated and assessed with the CALPHAD technique.The obtained results are in very good agreement with our experimental data and the published data reported in literature. The obtained thermodynamic database of Y-H system can be used to predict the hydrogenation behavior and decomposition temperatures of hydrides.     

Study on the hydrogen storage property of (TiZr0.1)xCr1.7-yFeyMn0.3 (1.05

Jigang Li  Li Xu  Xiaojing Jiang  Xingguo Li 《自然科学进展(英文版)》2018,28(4):470-477

CoPt-Co hybrid supported on amino modified SiO_2 nanospheres as a high performance catalyst for hydrogen generation from ammonia borane

CoPt-Co hybrids were successfully supported on amino modified SiO_2 nanospheres by a chemical reduction method at a temperature of 278 K.The solid carrier i.e.amino modified SiO_2,provides numerous anchoring sites for the metal nanoparticles(NPs)to improve the dispersion while reducing the size of metal NPs.The supported NPs displayed a narrow particle size distribution on the SiO_2 surface with an average diameter of 12 nm.The XRD results alongside with the binary alloy phase diagram suggest that the resulted NPs are bimetallic,composed of CoPt and amorphous Co.Among the prepared materials,the solid with the specific composition of SiO_2@Pt_(0.1)Co_(0.9)was proved to be effective catalyst for ammonia borane(AB)hydrolysis in aqueous solution.The turnover frequency(TOF)value of the supported nanocatalyst was 25.59mol_(H_2)min~(-1)·mol_M~(-1),almost twice as that of unsupported Pt_(0.1)Co_(0.9)NPs while the activation energy was 37.05 kJ mol~(-1).Furthermore,the SiO_2@Pt_(0.1)Co_(0.9)composite manifested high catalytic activity even after five cycles of reuse.     

Effect of Mg substitution for La on microstructure, hydrogen storage and electrochemical properties of La1−xMgxNi3.5 (x=0.20, 0.23, 0.25 at%) alloys

The effect of Mg substitution for La on microstructure, hydrogen storage and electrochemical properties of the annealed La_(1-x) Mg_x Ni_3.5(x=0.20, 0.23, 0.25 at%) alloys have been studied. All the samples were mainly composed of(LaMg)_2Ni_7,(LaMg)Ni_3, and LaNi_5 phases. Mg substitution for La changed the phase abundance, but did not change the constitution of all phases, which is con fi rmed by the results of backscattered SEM images and EDS analysis. The P–C isotherms indicated that the La_(1-x) Mg_x Ni_3.5alloys reversibly absorbed and desorbed hydrogen smoothly at 298 K. The hydrogen absorption cyclic stabilities of La_(1-x) Mg_x Ni_3.5alloy after 5 hydrogen absorption/desorption cycles reached the maximum values of91.9% and 96.0% at 298 K and 323 K, respectively. The hydrogen desorption capacity and plateau pressure for the La_(1-x) Mg_x Ni_3.5alloy reached the maximum values of 1.055 H/M and 0.074 MPa, respectively. The desorption capacities of La_(1-x) Mg_x Ni_3.5reached 0.193 H/M and 0.565 H/M in the fi rst minute at 298 K and 323 K, respectively. Electrochemical property measurement indicated that La_(1-x) Mg_x Ni_3.5(x=0.20,0.23, 0.25 at%) alloys possessed excellent activation capability and were completely activated within3 cycles. Discharge capacities of La_(1-x) Mg_x Ni_3.5alloys reached 378.2 m A h/g(x = 0.20 at%), 342.7 m A h/g(x = 0.23 at%), and 369.6 m A h/g(x = 0.25 at%), respectively. Moreover, energy density of La_(1-x) Mg_x Ni_3.5alloy was much larger than that of La_0.80Mg_0.20Ni_3.5 alloy and nearly approaches the maximum value of La0.75Mg0.25Ni3.5. Thus, the La_(1-x) Mg_x Ni_3.5alloy exhibits optimum comprehensive properties of hydrogen storage and electrochemistry.