Public debate on metallic hydrogen to boost high pressure research

Instead of praises from colleagues,the claim of observation of metallic hydrogen at 495 GPa by Dias and Silvera met much skepticism,and grew into a public debate at the International Conference on High-Pressure Science and Technology,AIRAPT26.We briefly review this debate,and extend the topic to show that this disputation could be an opportunity to benefit the whole high pressure community.

Synthesis,Structural Characterization and Hydrogen Storage of Nickel-containing Mesoporous MCM-48 by Electroless Plating

Hydrogen is a promising fuel for it is clean,highly abundant and non-toxic,but on-board storage of hydrogen is still a challenge.So it is imperative to have an efficient method of hydrogen storage.The mesoporous MCM-48 especially the nickel-containing MCM-48 has great potential in hydrogen storage.MCM-48 was prepared by hydrothermal synthesis.Then electroless plating technology was used to deposit Ni on the surface of MCM-48 under ultrasonic environment.Powder X-ray diffraction（XRD）,transmission electron microscopy（TEM）,and N2 adsorption-desorption were employed to investigate the pore structure properties.The results showed that all the samples had Ia3 d cubic structure and pore channels were highly ordered.Hydrogen adsorption studies showed that the MCM-48 after nickel plating adsorbed nearly twice the amount of hydrogen than pure MCM-48 at 2.0 MPa,263 K.So we believe that a small amount of Ni can improve the capacity of hydrogen adsorption of MCM-48 efficiently.

Electrocatalytic Activity of Ni/C Electrodes Prepared by Metal Vapor Synthesis For Hydrogen Evolution in Alkaline Solution

The metal vapor synthesis (MVS) methed was used to prepare activatedcarbon supported nickel electrode. The electrocatalytic activity of the electrode forhydrogen evolution reaction(HGR) in alkaline solution was studied. Cathodicpolarization curves showed the electrocatalytic activity of Ni/C electrode prepared byMVS method was higher than that of the one prepared by conventional method.

EFFECTS OF RARE EARTH METAL ON HYDROGEN BEHAVIOUR IN STEEL 16Mn

The slow tensile tests,dynamic hydrogen charging tensile tests and hydrogen evolution tests after hydrogen charging were used to study the effects of rare earth metal(REM)on hydrogen behaviour in a steel 16Mn(St.52).The ratios of RE/S were chosen as 0,0.7,2.2 and 7.7,respectively.It was shown that the steel with RE/S = 2.2 give a lower hydrogen embrittlement susceptibility than others.The steels without REM can adsorb much more amount of hydrogen than that with REM under the same hydrogen charging conditions.And the amount of adsorbed hydrogen for the foriner can be evolved easier than that for the latter at room temperature,50℃ and 80℃,respectively.The experimental results were explained by the trap theory of hydrogen,the short-circuit diffusion paths in the interfaces between the elongated MnS inclusions and the matrix,and strong ability of REM to adsorb hydrogen.

Selective Area Growth and Characterization of GaN Nanorods Fabricated by Adjusting the Hydrogen Flow Rate and Growth Temperature with Metal Organic Chemical Vapor Deposition

CaN nanorods are successfully fabricated by adjusting the flow rate ratio of hydrogen （H2）/nitrogen （N2） and growth temperature of the selective area growth （SAG） method with metal organic chemical vapor deposition （MOCVD）. The SAG template is obtained by nanospherical-lens photolithography. It is found that increasing the flow rate of 1-12 will change the CaN crystal shape from pyramid to vertical rod, while increasing the growth temperature will reduce the diameters of GaN rods to nanometer scale. Finally the CaN nanorods with smooth lateral surface and relatively good quality are obtained under the condition that the H2：N2 ratio is 1：1 and the growth temperature is 1030℃. The good crystal quality and orientation of GaN nanorods are confirmed by high resolution transmission electron microscopy. The cathodoluminescence spectrum suggests that the crystal and optical quality is also improved with increasing the temperature.

Theoretical Investigation for Two-state Reactivity of CO_2 Hydrogenation Catalyzed by Ru in Gas Phase

Gas-phase CO_2 catalyzed activation hydrogenation by Ru atoms was studied with density functional theory. Based on the structure optimization of different potential energy surfaces,there are two crossing points between singlet and triplet potential energy surfaces and there is a crossing point between quintet and triplet potential energy surfaces in the whole catalytic cycle. Spin transition probabilities in the vicinity of the intersections have been calculated by the Landau-Zener model theory. There are three minimum energy crossing points（MECPs） with strong spin-orbital coupling effect and higher spin transition probability,and all spin inversion occurred in s orbital and different d orbitals of ruthenium,indicating this is a typical two-state reactivity（TSR） reaction. Finally,the lowest energy reaction path is ensured.

Al(HSO_4)_3/silica gel as a novel catalytic system for the ring opening of epoxides with thiocyanate anion under solvent-free conditions

For the first time,metal hydrogen sulfates and phosphates/silica gel have been studied as efficient and powerful solid acid catalysts in the ring opening of epoxides with thiocyanate anion.The most significant result was obtained by Al(HSO4)3/SiO2which afforded the corresponding β-hydroxy thiocyanates under mild reaction conditions and in very short reaction times.The cheapness, availability of the catalyst,ease of procedure and work-up make this method attractive for the organic synthesis.

Thioetherification of isoprene and butanethiol on transition metal phosphides

Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal（Fe, Co, Ni, Mo and W） phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.

Effect of Preparation Technique on Microstructure and Hydrogen Storage Properties of LaNi(3.8)Al(1.0)Mn(0.2) Alloys

La Ni3.8Al1.0Mn0.2 alloy was prepared by vacuum induction melting and melt-spinning.The effects of different preparation techniques of the as-cast,cast then annealed,as-spun and spun then annealed alloys on the microstructure and hydrogen storage properties were investigated.The results indicated that the non-Ca Cu5 phases in the alloy became tinier and more dispersive after annealing or melt-spinning compared to those of the as-cast one.But in the spun then annealed alloy,the non-Ca Cu5 phases disappeared and only a single-phase with Ca Cu5 type structure was found.For all the alloys,the cell volume was increased in an order of as-cast 〈 spun then annealed 〈 cast then annealed 〈 as-spun,and the change of plateau pressure showed the opposite trend with that of the cell volume.The plateau could be flattened after melt-spinning or annealing,and the spun then annealed alloy showed the minimum plateau slope.The absorption kinetics of the alloy was promoted after melt-spinning or annealing.It is suggested that the change in cell volume and compositional homogeneity resulting from different preparation techniques contribute to the difference of the hydrogen storage properties of the investigated alloys.

Development and Application of Hydrogen Storage

Hydrogen,as a secure,clean,efficient,and available energy source,will be successfully applied to reduce and eliminate greenhouse gas emissions.Hydrogen storage technology,which is one of the key challenges in developing hydrogen economy,will be solved through the unremitting efforts of scientists.The progress on hydrogen storage technology research and recent developments in hydrogen storage materials is reported.Commonly used storage methods,such as high-pressure gas or liquid,cannot satisfy future storage requirement.Hence,relatively advanced storage methods,such as the use of metal-organic framework hydrides and carbon materials,are being developed as promising alternatives.Combining chemical and physical hydrogen storage in certain materials has potential advantages among all storage methods.Intensive research has been conducted on metal hydrides to improve their electrochemical and gaseous hydrogen storage properties,including their hydrogen storage capacity,kinetics,cycle stability,pressure,and thermal response,which are dependent on the composition and structural feature of alloys.Efforts have been exerted on a group of magnesium-based hydrides,as promising candidates for competitive hydrogen storage,to decrease their desorption temperature and enhance their kinetics and cycle life.Further research is necessary to achieve the goal of practical application by adding an appropriate catalyst and through rapid quenching or ball milling.Improving the kinetics and cycle life of complex hydrides is also an important aspect for potential applications of hydrogen energy.

Sodium-doped carbon nitride nanotubes for efficient visible light-driven hydrogen production

Sodium-doped carbon nitride nanotubes （Nax-CNNTs） were prepared by a green and simple two-step method and applied in photocatalytic water splitting for the first time. Transmission electron microscopy （TEM） element mapping and X-ray photoelectron spectroscopy （XPS） measurements confirm that sodium was successfully introduced in the carbon nitride nanotubes （CNNTs）, and the intrinsic structure of graphitic carbon nitride （g-C3N4） was also maintained in the products. Moreover, the porous structure of the CNNTs leads to relatively large specific surface areas. Photocatalytic tests indicate that the porous tubular structure and Na＋ doping can synergistically enhance the hydrogen evolution rate under visible light （λ 〉 420 nm） irradiation in the presence of sacrificial agents, leading to a hydrogen evolution rate as high as 143 μmol·h-1 （20 mg catalyst）. Moreover, other alkali metal-doped CNNTs, such as Lix-CNNTs and Kx-CNNTs, were tested; both materials were found to enhance the hydrogen evolution rate, but to a lower extent compared with the Nax-CNNTs. This highlights the general applicability of the present method to prepare alkali metal-doped CNNTs; a preliminary mechanism for the photocatalytic hydrogen evolution reaction in the Nax-CNNTs is also proposed.

Effect of ZnO Electrodeposited on Carbon Film and Decorated with Metal Nanoparticles for Solar Hydrogen Production

In this study, we prepared horn-like ZnO structures on carbon films（ZnO/CF） by electrodeposition and decorated the ZnO horns with different metals（Ag, Au, and Pt） via photodeposition（M-ZnO/CF）. Using M-ZnO/CF as photocatalysts, we examined ways to enhance solar hydrogen production from various points of view, such as modifying the intrinsic physical properties and thermodynamics of the materials, and varying the chemical environment during M-ZnO/CF fabrication. In particular, we focused on the effects of the carbon film and metals in M-ZnO/CF hybrid photocatalysts on solar hydrogen production. The type of metal nanoparticles is an important factor in solar hydrogen production because the deposition rate and electrical conductivity of each metal affect the proton-water reduction ability.

A two-dimensional microporous metal–organic framework for highly selective adsorption of carbon dioxide and acetylene

Solvothermal reaction of 3-aminoisonicotinic acid（Haina） and Cu（NO_3）_2·2.5H_2O gave a novel twodimensional（2D） microporous metal–organic framework, [Cu（aina）_2（DMF）]·DMF（1, DMF = N,N-dimethylformamide）. Single-crystal X-ray crystallographic study of compound 1 revealed that Cu（II）ions are linked by ainaàligands forming square grid-like layers, which stack together via multiple hydrogen bonding interactions. The solvent-free framework of 1a displayed considerable porosity（void = 46.5%） with one-dimensional（1D） open channels（4.7 ？ ？ 4.8 ？） functionalized by amino groups.Gas sorption measurements of 1 revealed selective carbon dioxide（CO_2） and acetylene（C_2H_2） adsorption over methane（CH_4） and nitrogen（N_2） at ambient temperature.