The effect of the carbon components on the performance of carbonbased transition metal electrocatalysts for the hydrogen evolution reaction

The hydrogen evolution reaction(HER)is a promising way to produce hydrogen,and the use of non-precious metals with an excellent electrochemical performance is vital for this.Carbon-based transition metal catalysts have high activity and stability,which are important in reducing the cost of hydrogen production and promoting the development of the hydrogen production industry.However,there is a lack of discussion regarding the effect of carbon components on the performance of these electrocatalysts.This review of the literature discusses the choice of the carbon components in these catalysts and their impact on catalytic performance,including electronic structure control by heteroatom doping,morphology adjustment,and the influence of self-supporting materials.It not only analyzes the progress in HER,but also provides guidance for synthesizing high-performance carbon-based transition metal catalysts.

Investigation of Coercivity Mechanism for Nd-Fe-B Magnets Prepared by Combination of Strip-Casting with Hydrogen Decrepitation Techniques

The coercivity mechanism of Nd Fe B magnets prepared by combination of strip casting with hydrogen decrepitation techniques was investigated. The microstructure of (Nd 0.935 Dy 0.065 ) 14.5 Fe 79.4 B 6.1 magnet was observed. The average grain size is about 6～12 μm. The magnetizing field dependence of the hardmagnetic properties for the (Nd 0.935 Dy 0.065 ) 14.5 Fe 79.4 B 6.1 and the temperature dependence of the coercivity for the Nd 14.5 Fe 79.4 B 6.1 were investigated. Results show that the coercivity for magnets prepared by the combination of strip casting with hydrogen decrepitation techniques is controlled by the nucleation mechanism.

Phase transformation behavior of a TiNiCu shape memory alloy electro-lytically charged with hydrogen

The transformation behavior of a TiNiCu shape memory alloy electrolyticallycharged with hydrogen was investigated by means of different scanning calorimetry (DSC), opticalmicroscope and X-ray diffraction (XRD). The results showed that inter- and inner-granular hydridesformed after charging with hydrogen, and the hydrides suppressed martensitic transformation. Theelectrolytically charged hydrogen can be easily released by heat treatment and the transformationoccurred again, which was verified by the DSC and XRD experiments.

Confined synthesis of MoS_(2) with rich co-doped edges for enhanced hydrogen evolution performance

Activating MoS_(2) with atomic metal doping is promising to harvest desirable Pt-matched hydrogen evolution reaction(HER)catalytic performance.Herein,we developed an efficient method to access edgerich lattice-distorted MoS_(2) for highly efficient HER via in-situ sulphuration of atomic Co/Mo species that were well-dispersed in a formamide-derived N-doped carbonaceous(f-NC)substrate.Apart from others,pre-embedding Co/Mo species in f-NC controls the release of metal sources upon annealing in S vapor,grafting the as-made MoS_(2) with merits of short-range crystallinity,distorted lattices,rich defects,and more edges exposed.The content of atomic Co species embedded in MoS_(2) reaches up to 2.85 at.%,and its atomic dispersion has been systematically confirmed by using XRD,HRTEM,XPS,and XAS characterizations.The Co-doped MoS_(2) sample exhibits excellent HER activity,achieving overpotentials of 67 and155 m V at j=10 m A cm^(-2) in 1.0 M KOH and 0.5 M H_(2)SO_(4),respectively.Density functional theory simulations suggest that,compared with free-doping MoS_(2),the edged Co doping is responsible for the significantly improved HER activity.Our method,in addition to providing reliable Pt-matched HER catalysts,may also inspire the general synthesis of edge-rich metal-doped metal chalcogenide for a wide range of energy conversion applications.

Recent advances in the electrochemistry of layered post-transition metal chalcogenide nanomaterials for hydrogen evolution reaction

Layered two-dimensional(2 D)materials have received tremendous attention due to their unique physical and chemical properties when downsized to single or few layers.Several types of layered materials,especially transition metal dichalcogenides(TMDs)have been demonstrated to be good electrode materials due to their interesting physical and chemical properties.Apart from TMDs,post-transition metal chalcogenides(PTMCs)recently have emerged as a family of important semiconducting materials for electrochemical studies.PTMCs are layered materials which are composed of post-transition metals raging from main group IIIA to group VA(Ga,In,Ge,Sn,Sb and Bi)and group VI chalcogen atoms(S,selenium(Se)and tellurium(Te)).Although a large number of literatures have reviewed the electrochemical and electrocatalytic applications of TMDs,less attention has been focused on PTMCs.In this review,we focus our attention on PTMCs with the aim to provide a summary to describe their fundamental electrochemical properties and electrocatalytic activity towards hydrogen evolution reaction(HER).The characteristic chemical compositions and crystal structures of PTMCs are firstly discussed,which are different from TMDs.Then,inherent electrochemistry of PTMCs is discussed to unveil the well-defined redox behaviors of PTMCs,which could potentially affect their efficiency when applied as electrode materials.Following,we focus our attention on electrocatalytic activity of PTMCs towards HER including novel synthetic strategies developed for the optimization of their HER activity.This review ends with the perspectives for the future research direction in the field of PTMC based electrocatalysts.

Impact of preparation conditions on hydrogen storage performance of metallic Ti-doped NaAlH_4

Contrary to the popular opinion, it has been found that metallic Ti powder can be directly utilized as dopant precursor to prepare catalytically enhanced NaAlH4 through mechanical milling. As a novel method for preparation of catalytically enhanced NaAlH4, direct metallic Ti-doping possesses practical advantage over the state-of-the-art doping technology: elimination of the inactive by-products and the gas impurities that are highly detrimental to fuel cell operation. A systematic investigation along this new approach was performed under various preparation conditions, including different starting materials, milling atmosphere and milling time. The materials thus prepared under different conditions were found to share some common features, while at the meantime, differ significantly from each other on hydrogen storage performance. A comprehensive understanding of these results provides valuable insight into a series of fundamental questions in catalytically enhanced Ti-NaAlH4 system.

Mg-based materials for hydrogen storage

Over the last decade’s magnesium and magnesium based compounds have been intensively investigated as potential hydrogen storage as well as thermal energy storage materials due to their abundance and availability as well as their extraordinary high gravimetric and volumetric storage densities.This review work provides a broad overview of the most appealing systems and of their hydrogenation/dehydrogenation properties.Special emphasis is placed on reviewing the efforts made by the scientific community in improving the material’s thermodynamic and kinetic properties while maintaining a high hydrogen storage capacity.

Hydrogen Absorption and Release Behavior in Hydrogen Decrepitation Process of Nd-Fe-B Alloys

The behavior of hydrogen absorption and release in hydrogen decrepitation (HD) process of Nd Fe B alloys were investigated. The results reveal that the reactivity and the amount of hydrogen absorption in HD process are related to the surface activity of the alloy so that the fresh and active surface has a higher efficiency. The presence of Nd rich phase at the grain boundary is an essential factor of the HD activity of the alloy at room temperature. On degassing, hydrogen is released from the HD powder continuously with increasing temperature. And the residual hydrogen is as low as 0 0015% at 1073 K, which shows that the hydrogen is almost exhaused. It is feasible to remove the hydrogen from the HD powder by heating treatment at the temperature of 523～723 K for 1 h prior to the magnetic field forming in order to decrease the harmful effect of hydrogen on the easy axis alignment of HD magnet.

Underwater Laser Welding/Cladding for High-performance Repair of Marine Metal Materials:A Review

With the rapid developments of marine resource exploitation,mounts of marine engineering equipment are settled on the ocean.When it is not possible to move the damaged equipment into a dry dock,welding operations must be performed in underwater environments.The underwater laser welding/cladding technique is a promising and advanced technique which could be widely applied to the maintenance of the damaged equipment.The present review paper aims to present a critical analysis and engineering overview of the underwater laser welding/cladding technique.First,we elaborated recent advances and key issues of drainage nozzles all over the world.Next,we presented the underwater laser processing and microstructural-mechanical behavior of repaired marine materials.Then,the newly developed powder-feeding based and wire-feeding based underwater laser direct metal deposition techniques were reviewed.The differences between the convection,conduction,and the metallurgical kinetics in the melt pools during underwater laser direct metal deposition and in-air laser direct metal deposition were illustrated.After that,several challenges that need to be overcame to achieve the full potential of the underwater laser welding/cladding technique are proposed.Finally,suggestions for future directions to aid the development of underwater laser welding/cladding technology and underwater metallurgical theory are provided.The present review will not only enrich the knowledge in the underwater repair technology,but also provide important guidance for the potential applications of the technology on the marine engineering.

Catalyst activation: Surface doping effects of group Ⅵ transition metal dichalcogenides towards hydrogen evolution reaction in acidic media

Two-dimensional(2D) transition metal dichalcogenides(TMDs) have emerged as promising alternatives to the platinum-based catalysts for hydrogen evolution reaction(HER). The edge site of these2D materials exhibits HER-active properties, whereas the large-area basal plane is inactive.Therefore, recent studies and methodologies have been investigated to improve the performance of TMD-based materials by activating inactive sites through elemental doping strategies. In this review,we focus on the metal and non-metal dopant effects on group VI TMDs such as MoS_(2) MoSe_(2) WS_(2)and WSe_(2) for promoting HER performances in acidic electrolytes. A general introduction to the HER is initially provided to explain the parameters in accessing the catalytic performance of dopedTMDs. Then, synthetic methods for doped-TMDs and their HER performances are introduced in order to understand the effect of various dopants including metallic and non-metallic elements. Finally, the current challenges and future opportunities are summarized to provide insights into developing highly active and stable doped-TMD materials and valuable guidelines for engineering TMD-based nanocatalysts for practical water splitting technologies.

High volumetric hydrogen density phases of magnesium borohydride at high-pressure:A first-principles study

The previously proposed theoretical and experimental structures, bond characterization, and compressibility of Mg（BH4）2 in a pressure range from 0 to 10 GPa are studied by ab initio density-functional calculations. It is found that the ambient pressure phases of meta-stable I41/amd and unstable P-3ml proposed recently are extra stable and cannot decompose under high pressure. Enthalpy calculation indicates that the ground state of F222 structure proposed by Zhou et al. [2009 Phys. Rev. B 79 212102] will transfer to I41/amd at 0.7 GPa, and then to a P-3ml structure at 6.3 GPa. The experimental P6122 structure （a-phase） transfers to I41/amd at 1.2 GPa. Furthermore, both I41/arnd and P-3ml can exist as high volumetric hydrogen density phases at low pressure. Their theoretical volumetric hydrogen densities reach 146.351 g H2/L and 134.028 g H2/L at ambient pressure, respectively. The calculated phonon dispersion curve shows that the I41/amd phase is dynamically stable in a pressure range from 0 to 4 CPa and the P-3ral phase is stable at pressures higher than 1 GPa. So the I41/arnd phase may be synthesized under high pressure and retained to ambient pressure. Energy band structures show that they are both always ionic crystalline and insulating with a band-gap of about 5 eV in this pressure range. In addition, they each have an anisotropic compressibility. The c axis of these structures is easy to compress. Especially, the c axis and volume of P-3ml phase are extraordinarily compressible, showing that compression along the e axis can increase the volumetric hydrogen content for both I41/amd and P-3ml structures.

Synthesis of nanostructured Mg_2FeH_6 hydride and hydrogen sorption properties of complex

Reactive mechanical alloying(RMA)was carried out in a planetary ball mill for the synthesis of ternary hydride Mg2FeH6 for hydrogen storage.The formation mechanism of Mg2FeH6 in RMA process and the sorption properties of the products were investigated.The results show that Mg2FeH6 has a yield ratio around 80%,and a grain size below 10 nm in the powder synthesized by milling 3Mg+Fe mixture for 150 h under the hydrogen pressure of 1 MPa.The synthesized powder possesses a high hydrogen capacity and good sorption kinetics,and absorbs 4.42%(mass fraction)of hydrogen within 200 s at 623 K under the hydrogen pressure of 4.0 MPa.In releasing hydrogen at 653 K under 0.1 MPa,it desorbs 4.43%(mass fraction)of hydrogen within 2 000 s.The addition of Ti increases the hydrogen desorption rate of the complex in the initial 120 s of the desorption process.

Phase Structure and Electrochemical Properties of RE-Mg Based Composite Hydrogen Storage Alloys

A new type of AB_5-x%LaMg_3(x=2, 3, 4, 5, 6, 7, 8)composite hydrogen storage alloys were prepared by sintering the powder mixtures of a commercial AB_5 alloy and LaMg_3 alloy. The phase structure and electrochemical characteristics of the composite hydrogen storage alloys were also studied. It is shown that AB_(5)-x%LaMg_3(x=2, 3, 4, 5, 6, 7, 8)composites have mult; phase structure. The matrix phase has CaCu_5 structure, the second phase is LaNi_3 phase. The maximum discharge capacity, discharge capacity at low temperature and HRD of AB_5 alloy electrodes are greatly improved after the composite. The maximum discharge capacity of the composite electrodes increases from 325 mAh·g^(-1) for x=0 to 358 mAh·g^(-1) for x=5, and the HRD of the composites for x=5 at the current density of 1200 mA·g^(-1)30% of that of the alloy at 60 mA·g^(-1). The discharge capacity of AB_5-x%LaMg_3 composite alloy electrode at 233 K is up to 174 mAh·g^(-1). The improvement of the electrochemical characteristics of the composite electrodes seems to be related with formation of the LaNi_3 second phase.

Evolution of Sm2Fel7 Alloys during Hydrogenation-Disproportion Process

The evolution of phase compositions, phase change and microstructure in Sm2Fe17 alloys during hydrogenationdisproportion process were systematically studied with XRD, SEM, EDX methods. Research indicates that HD process of Sm2Fe17 alloys is as follows： Sm2Fe17 alloy absorbs hydrogen first in the atmosphere of hydrogenation with a pressure of 0.1 MPa. Disproportionation begins at T ≥ 500 ℃, then the alloys tuna into lots of SmHx and α-Fe phases which are partly in microcrystal or amorphous structures. Along with the increase of temperature, the microcrystal and amorphous structures transformed into crystal structure and this transformation thoroughly completed at 750 ℃. The size of obtained crystal grain is about 20 - 100 nm. Based on the experimental data, a microstructural transformation model of Sm2Fe17 alloys during hydrogenation-disproportion process was made.

Hydrogen Absorption of Nd-Fe-B Alloys

The technical parameters of HD process were studied, including the effects of temperature and neodymium contents on the incubation period of hydrogen absorption, hydrogen concentration and the rate of hydrogen absorbed. The results show that the incubation period is shortened and the rate of hydrogen absorbed is accelerated with rising temperature and surface area. These are attributed to the rising rate of hydrogen diffusion at higher temperature. The change of the incubation period and the rate of hydrogen absorbed have the similar trend resulted from the increasing content of the Nd-rich phase owing to the rising temperature. Moreover, the percent of the Nd-rich phase in the ingot can be calculated according to the total hydrogen weight gain.

Hydrogen Embrittlement Processes and Al/Al_2O_3 Hydrogen Resistance Coatings of NdFeB Magnets

After analyzing the phenomena and processes of hydrogen embrittlement of NdFeB permanent magnets, RF magnetron sputtering was used to fabricate Al thin films and then oxidized to form the Al/Al_2O_3 composite films on the magnets as the hydrogen resistance coatings. SEM and EDS were used to examine the morphology and composition respectively. Hydrogen resistance performance was tested by exposing the magnets in 10 MPa hydrogen gas at room temperature. The results show that the magnets with 8 μm Al/Al_2O_3 coatings can withstand hydrogen of 10 MPa for 65 min without being embrittled into powder. The samples with and without hydrogen resistance coatings have almost the same magnetic properties.

掺氢输送管道材料的适应性及评价方法

天然气管网掺氢输送可有效解决氢能利用过程中的输送问题,但这会给管道带来安全风险。本文详细评述了掺氢输送管道金属和非金属材料的种类、适应性影响因素及其评价方法,建议完善和利用现有金属和非金属材料宏观性能表征及微观机理分析方法,结合实际工况环境及材料关键性能指标,建立掺氢输送管道的适应性评价方法和评价限值要求,并完善实际掺氢试运行评价方法和评判标准。本文可为天然气管网掺氢输送工程提供重要参考。

金属磷化物在电解水制氢中的应用研究进展

电解水被认为是目前最有前途的制氢方法之一。基于商用贵金属基催化剂成本高和储量有限的情况,开发低成本、高性能的电催化剂是实现电解水制氢产业化的关键。过渡金属磷化物因具有独特的物化性质和高催化活性而被广泛关注,但导电性和活性位点密度的不足限制了其在工业化制氢中的应用。首先阐述电解水析氢的机理及过渡金属磷化物的重要作用。然后从单金属磷化物、双金属磷化物、改性金属磷化物和结构调控过渡金属磷化物4个方面分析不同种类的过渡金属磷化物以及提升其催化性能的途径,并比较了当前过渡金属磷化物的常用制备方法。最后总结提升催化性能的主要策略,展望过渡金属磷化物未来的机遇和挑战。期望本综述有助于过渡金属磷化物电催化剂的设计开发与应用。

镍基磷化物复合材料在催化电解水析氢性能提升方面的研究进展

镍基磷化合物因其自身的类氢化酶电子结构和其出色的稳定性被证明具有良好的电解水析氢能力。单金属磷化物因其本征活性不足、导电性不高及稳定性较差等问题,使其在实际应用上受到了限制。综述了结构新颖、性能优异和稳定性高的镍基磷化物复合材料的研究进展,总结和分析了通过杂原子掺杂、形貌调控、结合自支撑材料和复合新型材料(碳纳米管、石墨烯、石墨炔、二维材料MXene)等方式在调控催化材料的电子结构、微观形貌、促进长时间电解稳定性、增大比表面积和提高导电性方面提升电解水析氢性能的研究成果。为探索催化活性高和结构稳定兼备的新型镍基磷化物复合材料提供研究方向。

金属-有机框架物(MOFs)储氢材料研究进展

介绍了一种新型储氢材料——金属-有机框架物(Metal-organic framework,MOFs)。该材料具有许多优异的性能,如密度小、比表面积大、气孔率高等,并可通过组装来控制框架物的结构和孔径的大小,是一种具有发展前景的新型储氢材料。在总结、评述MOFs储氢材料制备、表征、储氢性能及其影响因素等研究进展的基础上提出了今后的研究重点和发展方向。