Note: Times Cited: 875 Reference EPFL-ARTICLE-206025doi:10.1021/cr0501846View record in Web of Science URL: ://WOS:000249839900009 Record created on 2015-03-03, modified on 2017-05-12

Complex Hydrides for Hydrogen Storage

DOI: 10.1002/aenm.201800369 reactions involved.[1] In recent years, tremendous progress has been achieved in the field of heterogeneous electrocatalysis, with rapid development of multifarious electocatalysts toward oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and carbon dioxide reduction reaction (CO2RR). However, electrocatalysts for the reduction of dinitrogen (N2) to ammonia (NH3) at room temperature and atmospheric pressure remain largely underexplored, despite the fact that investigations on catalysts and reaction systems for artificial nitrogen fixation have been continued for more than 100 years.[2–4] Ammonia is primarily used for producing fertilizers to sustain the world’s population.[5] It also serves as a green energy carrier and a potential transportation fuel.[6] Currently, ammonia synthesis is dominated by the industrial Haber–Bosch process using heterogeneous iron-based catalysts at high temperature (300–500 °C) and high pressure (150–300 atm),[7] accounting for more than 1% of the world’s energy supply and generating more than 300 million metric tons of fossil fuel–derived CO2 annually.[8,9] Hence, it is desirable to develop alternative processes that have the potential to overcome the limitations of the Haber–Bosch process including harsh conditions, complex plant infrastructure, centralized distribution, high energy consumption, and negative environmental impacts. In nature, biological N2 fixation occurs under mild conditions via nitrogenase enzymes that contain FeMo, FeV, or FeFe cofactor as catalytic active sites.[10,11] Developed man-made catalysts are therefore stimulated to reduce N2 upon the addition of protons and electrons, which is similar to the nitrogenase catalytic process. Transition metal–dinitrogen complexes such as the molybdenum–, iron–, and cobalt–dinitrogen complexes have been proposed as homogeneous catalysts for the reduction of N2 into NH3 under ambient conditions;[12] however, the stability and recycling issues are challenging.[13] On the other hand, electrochemical and photochemical reduction processes using heterogeneous catalysts benefit from clean and renewable energy sources and are promising for achieving NH3 production directly from N2 and water.[14] The electrochemical reduction of N2 to NH3 can be more efficient than the photochemical counterpart. This is because not all of the photons in the photochemical reduction process can The production of ammonia (NH3) from molecular dinitrogen (N2) under mild conditions is one of the most attractive topics in the field of chemistry. Electrochemical reduction of N2 is promising for achieving clean and sustainable NH3 production with lower energy consumption using renewable energy sources. To date, emerging electrocatalysts for the electrochemical reduction of N2 to NH3 at room temperature and atmospheric pressure remain largely underexplored. The major challenge is to achieve both high catalytic activity and high selectivity. Here, the recent progress on the electrochemical nitrogen reduction reaction (NRR) at ambient temperature and pressure from both theoretical and experimental aspects is summarized, aiming at extracting instructive perceptions for future NRR research activities. The prevailing theories and mechanisms for NRR as well as computational screening of promising materials are presented. State-of-the-art heterogeneous electrocatalysts as well as rational design of the whole electrochemical systems for NRR are involved. Importantly, promising strategies to enhance the activity, selectivity, efficiency, and stability of electrocatalysts toward NRR are proposed. Moreover, ammonia determination methods are compared and problems relating to possible ammonia contamination of the system are mentioned so as to shed fresh light on possible standard protocols for NRR measurements.

A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions

A review on the current progress of metal hydrides material for solid-state hydrogen storage applications

Global ammonia production reached 175 million metric tons in 2016, 90% of which is produced from high purity N2 and H2 gases at high temperatures and pressures via the Haber-Bosch process. Reliance on natural gas for H2 production results in large energy consumption and CO2 emissions. Concerns of human-induced climate change are spurring an international scientific effort to explore new approaches to ammonia production and reduce its carbon footprint. Electrocatalytic N2 reduction to ammonia is an attractive alternative that can potentially enable ammonia synthesis under milder conditions in small-scale, distributed, and on-site electrolysis cells powered by renewable electricity generated from solar or wind sources. This review provides a comprehensive account of theoretical and experimental studies on electrochemical nitrogen fixation with a focus on the low selectivity for reduction of N2 to ammonia versus protons to H2. A detailed introduction to ammonia detection methods and the execution of control experiments is given as they are crucial to the accurate reporting of experimental findings. The main part of this review focuses on theoretical and experimental progress that has been achieved under a range of conditions. Finally, comments on current challenges and potential opportunities in this field are provided.

Recent Advances and Challenges of Electrocatalytic N2 Reduction to Ammonia.

Hydrogen storage systems (HSSs), are the backbone of feasible hydrogen economy. To provide a reliable renewable energy system, safe, cost effective and compact HSS is due. Physical storage systems involve the compressed gas, liquid and cryo-compressed techniques while material based one involves adsorptive materials, metal hydrides and chemical storage materials. In this paper, the features of a variety of HSSs are impartially discussed. The technical comparative analysis of the different physical and material based types of HSSs illustrates the paradoxical inherent features, including gravimetric and volumetric storage densities and parameters associated with storage and release processes, among these systems. Accordingly, no ideal hydrogen storage technique can be considered the best-fit for all stationary and automotive applications. Therefore, not only a unique HSS solution can properly provide the needs, but a set of complementary HSS solutions which may offer the system designer several options. This set of options can be hardly interpretable in case of the unclear definition of the application needs which may be time variant. Inside this review, the critical insights and recommendations about suitable applications for storage systems are provided. Different standards and codes alongside the corresponding tests are demonstrated for the different storage technologies. Moreover, storage vessels research work is overviewed for the different hydrogen storage technologies. In addition, the failure behaviour, criteria and prediction models are investigated for composite vessels subjected to high pressures and extreme temperatures degrading their mechanical behaviour and failure resistance.

Hydrogen storage technologies for stationary and mobile applications: Review, analysis and perspectives

The metallic vanadium has an excellent hydrogen storage properties in comparison to other hydride forming metals such as titanium, uranium, and zirconium. The gravimetric storage capacity of vanadium is over 4 wt% which is even better than AB2 and AB5 alloys. The metallic vanadium has shown high hydrogen solubility and diffusivity at nominal temperature and pressure conditions. Consequently, vanadium is under consideration for the cost-effective hydrogen permeation membrane to replace palladium. The issues with vanadium are poor reversibility and pulverization. The poor reversibility is because of high thermal stability of β (VH/V2H) phase which eventually restricts the cyclic hydrogen storage capacity up to 2 wt% at room temperature. The pulverization is because of large crystal misfit between the metal and metal hydride phase. The hydrogen solubility, phase stability, hydrogenation-dehydrogenation kinetics, and pulverization are highly influenced by the presence of an alloying element. Therefore, worldwide efforts are to explore and optimize the alloying element which could enhance the hydrogen solubility, destabilized the β phase, improved the hydrogenation-dehydrogenation kinetics, and prevent the pulverization. The current review is a systematic presentation of these efforts to resolve the issues of vanadium as a base material for hydrogen storage and permeation membrane.

Development of vanadium based hydrogen storage material: A review

Magnesium hydride and its complex variants, i.e. Mg(AlH4)2 and Mg(BH4)2 are known for their high hydrogen capacity. The theoretical capacities of these three are 7.6 wt%, 9.3 wt% and 14.4 wt%, respectively. In spite of having very attractive H2 capacities, their high operating temperature, i.e. more than 300 °C and sluggish kinetics are big issues to be solved before these can be realized for a practical hydrogen storage system. There are several efforts devoted to reduce the working temperature and enhance the sorption kinetics using various additives. Ti-based additives have always been interesting contenders in enhancing the kinetics as well as altering thermodynamics thus reducing the working temperature for various hydrides. Recently, TiF4 has shown superior catalytic activity on the decomposition of Mg(AlH4)2. This motivates us to study its effect on the decomposition of all the above-mentioned Mg-based hydrides. It is observed that the addition of 10 wt% TiF4 to the above materials greatly influences the decomposition temperature. The decomposition temperature for all three reactions is shifted to the lower temperature side. The oxidation state of the catalyst surface has been investigated using the XPS technique and then the detailed mechanism associated with this improvement is proposed herein.

Sanjay Kumar

Papers

Development of vanadium based hydrogen storage material: A review

How does TiF4 affect the decomposition of MgH2 and its complex variants? – An XPS investigation

Surface modification of MgH2 by ZrCl4 to tailor the reversible hydrogen storage performance

The enhanced de/re-hydrogenation performance of MgH2 with TiH2 additive

High performance FeTi – 3.1 mass % V alloy for on board hydrogen storage solution