Deep insight of unique phase transition behaviors and mechanism in Zr_(2)Co-H isotope system with ultra-low equilibrium pressure

Efficient capture,safe storage and release of tritium from the international thermonuclear experimental reactor(ITER) reaction exhaust gas is a perplexing problem,and the development of an efficient tritium-getter material with ultra-low hydrogenation equilibrium pressure is considered as a reliable way.In this work,Zr_(2)Co alloy was selected as a tritium-getter material and prepared through induction levitation melting.Fundamental performance test results show that Zr_(2)Co exhibits an ultra-low hydrogenation equilibrium pressure of 3.22 × 10^(-6) Pa at 25℃ and excellent hydriding kinetics under a low hydrogen pressure of 0.005 MPa.Interestingly,unique phase transition behaviors were presented in Zr_(2)Co-H system.Specifically,Zr_(2)CoH_(5) formed by Zr_(2)Co hydrogenated at room temperature is initially decomposed into ZrH_(2) and ZrCoH_(3) at200 ℃.With the temperature increasing to 350 ℃,ZrCoH_(3)is dehydrogenated to ZrCo,and then ZrCo further reacts with ZrH_(2) at 650 ℃ to reform Zr_(2)Co and hydrogen.Among the staged phase transition pathways during dehydrogenation,the decomposition of Zr_(2)CoH_(5) occurs preferentially,which is well accordance with both the smallest reaction energy barrier and the maximum reaction spontaneity that are determined respectively from kinetics activation energy and thermodynamics Gibbs free energy.Furthermore,first principles calculation results indicate that the stronger binding of hydrogen in interstitial environments of ZrCoH_(3)and ZrH_(2) triggers the hydrogen-stabilized phase transformation of Zr_(2)CoH_(5).The unique phase transition mechanisms in Zr_(2)Co-H system can shed light on the further exploration and regulation of analogous staged phase transition of hydrogen storage materials.

Enhanced hydrogen evolution performance by 3D ordered macroporous Ru-CoP@NC electrocatalysts

Electrocatalytic water splitting coupled with sustainable energies is identified as an environmentally friendly and renewable strategy to generate high-quality hydrogen for the fuel cells.However,the main challenge is to develop high performance,low cost and chemically stable electrocatalysts to decline the energy barriers and enhance the sluggish kinetics of hydrogen evolution reaction(HER).Herein,a three-dimensional hierarchically ordered macroporous Ru-CoP@NC electrocatalyst(3DOM Ru-CoP@NC)derived from ordered macro-microporous metal-organic frameworks has been prepared using the precursor@template and double-solvent methods.The prepared 3DOM Ru-CoP@NC catalyst exhibits an overpotential of 15 mV(j=10 mA·cm^(-2))and a reaction Tafel slope of 38 mV·dec^(-1)in alkaline electrolyte,which are superior to commercial Pt@C catalyst.Additionally,the overpotential and reaction Tafel slope of this catalyst in acidic media are 45 mV and 50 mV·dec^(-1),respectively.The outstanding HER activities of 3DOM Ru-CoP@NC catalysts are ascribed to the 3D highly interconnectedreticular nanospaces that can increase effective reaction active sites.The N dope d carbon framework improves the electronic properties and conductivity.Moreover,the strong interaction of Ru and CoP nanoparticles also boosts the HER process.These results indicate that 3DOM Ru-CoP@NC catalysts with high catalytic activities have a broad application prospect in the future.

Synthesis of nanoscale CeAl4 and its high catalytic efficiency for hydrogen storage of sodium alanate

Nanoscale CeAl4 was directly synthesized by the thermal reaction between CeH2 and nano-aluminum at300℃.Then nano CeAl4-doped sodium alanate（NaAlH4）was synthesized by ball milling NaH/Al with 0.04CeAl4under hydrogen atmosphere at room temperature,and the catalytic efficiency of nanoscale CeAl4 for hydrogen storage of NaAlH4 was systematically investigated.It is shown that CeAl4 can effectively improve the dehydrogenation properties of sodium alanate system.The 0.04CeAl4-doped NaAlH4 system starts to release hydrogen below 80℃,completes dehydrogenation within 10 min at 170℃,and exhibits good cycling de/hydrogenation kinetics at relatively lower temperature（100-140℃）.Apparent activation energy of the dehydrogenation of NaAlH4 can be effectively reduced by addition of CeAl4,resulting in the decrease in desorption temperatures.Moreover,by analyzing the reaction kinetics of nano CeAl4-doped NaAlH4sample,both of the decomposition steps are conformed to a two-dimensional phase-boundary growth mechanism.The mechanistic investigations gained here can help to understand the de-/rehydrogenation behaviors of catalyzed complex metal hydride systems.

Development of Ti_(0.85)Zr_(0.17)(Cr-Mn-V)_(1.3)Fe_(0.7)-based Laves phase alloys for thermal hydrogen compression at mild operating temperatures

Metal hydride with proper hydrogen storage properties is the key component of hydride thermal hydrogen compressor.In this work,Ti_(0.85)Zr_(0.17)(Cr-Mn-V)_(1.3)Fe_(0.7)-based alloys were developed to achieve thermal hydrogen compression at mild operating temperatures of water bath.The results indicate the single C 14-type Laves phase as well as homogeneously distributed elements of all alloys.With increased Mn content in Ti_(0.85)Zr_(0.17)Cr_(1.2-x)Mn_xFe_(0.7)V_(0.1)(x=0,0.1,0.2,0.3)alloys.