Light-Driven De/Rehydrogenation of a LiH Surface under Ambient Conditions.

Lithium hydride (LiH), a saline hydride with a hydrogen density of 12.6 wt %, is highly thermostable, which hinders its extensive application in hydrogen storage. In this study, we demonstrate a distinct photodecomposition of LiH under ambient conditions. Ultraviolet-visible (UV-vis) illumination induces hydrogen release and creates surface hydrogen vacancies on LiH. The subsequent H- migration enables hydrogen desorption and the accumulation of vacancies at the subsurface, resulting in the generation of metallic Li clusters. Rehydrogenation, on the contrary, can be charged under UV-vis illumination in 1 bar H2. Such phenomena show that the thermodynamic and kinetic limits in the re/dehydrogenation of LiH can be broken under illumination, which allows hydrogen storage over the LiH surface at temperatures ∼600 K lower than those of the corresponding thermal process. This work provides new insights into the interaction of semiconducting hydrides and photons and opens an avenue for the development and optimization of materials for hydrogen storage and related photodriven reactions.

Light-driven ammonia synthesis under mild conditions using lithium hydride.

Photon-driven chemical processes are usually mediated by oxides, nitrides and sulfides whose photo-conversion efficiency is limited by charge carrier recombination. Here we show that lithium hydride undergoes photolysis upon ultraviolet illumination to yield long-lived photon-generated electrons residing in hydrogen vacancies, known as F centres. We demonstrate that photon-driven dehydrogenation and dark rehydrogenation over lithium hydride can be fulfilled reversibly at room temperature, which is about 600 K lower than the corresponding thermal process. As light-driven F centre generation could provide an alternative approach to charge carrier separation to favour chemical transformations that are kinetically or thermodynamically challenging, we show that light-activated lithium hydride cleaves the N≡N triple bond to form a N-H bond under mild conditions. Co-feeding a N2/H2 mixture with low H2 partial pressure leads to photocatalytic ammonia formation at near ambient conditions. This work provides insights into the development of advanced materials and processes for light harvesting and conversion.

Deforming lanthanum trihydride for superionic conduction.

With strong reducibility and high redox potential, the hydride ion (H-) is a reactive hydrogen species and an energy carrier. Materials that conduct pure H- at ambient conditions will be enablers of advanced clean energy storage and electrochemical conversion technologies1,2. However, rare earth trihydrides, known for fast H migration, also exhibit detrimental electronic conductivity3-5. Here we show that by creating nanosized grains and defects in the lattice, the electronic conductivity of LaHx can be suppressed by more than five orders of magnitude. This transforms LaHx to a superionic conductor at -40 °C with a record high H- conductivity of 1.0 × 10-2 S cm-1 and a low diffusion barrier of 0.12 eV. A room-temperature all-solid-state hydride cell is demonstrated.

Catalyst-free synthesis of lithium hydride at room temperature.

An organic solvent-assisted catalyst-free mechanochemical reaction is developed to synthesize lithium hydride at mild gas pressures and room temperature. Studies show that the formation of intermediates on the surface of bulk lithium metal is crucial for the synthesis of high purity (>98%) LiH. This provides a new strategy for the large-scale production of lithium-based hydrogen storage materials.

One-Step Synthesis of Light Metal Nanoparticle from Metastable Complex.

Metal nanoparticles have attracted considerable scientific and technological interest in recent years, most related explorations and reports are focused on transition and noble metals. However, the synthesis and application of light metal nanoparticles represented by Mg have not been fully exploited, limited by their ultrahigh reactivity in air and preparation in harsh conditions. In this work, a simple and effective one-step organic solvent-assisted ball-milling process is developed to synthesize Mg and Li nanoparticles, which permits the formation of MgH2 in a hydrogen atmosphere in a one-step reaction process at ambient temperature. Further studies suggest that acetone chemisorbs on defects/surfaces of Mg during ball milling leading to the formation of a metastable magnesium complex, which significantly alters the physical and chemical characteristics of Mg grains. The formation of metastable complexes provides an attractive strategy to produce light metal nanoparticles and inspires the authors to study the interaction of organic solvents with light metals.

Technologies and perspectives for achieving carbon neutrality.

Global development has been heavily reliant on the overexploitation of natural resources since the Industrial Revolution. With the extensive use of fossil fuels, deforestation, and other forms of land-use change, anthropogenic activities have contributed to the ever-increasing concentrations of greenhouse gases (GHGs) in the atmosphere, causing global climate change. In response to the worsening global climate change, achieving carbon neutrality by 2050 is the most pressing task on the planet. To this end, it is of utmost importance and a significant challenge to reform the current production systems to reduce GHG emissions and promote the capture of CO2 from the atmosphere. Herein, we review innovative technologies that offer solutions achieving carbon (C) neutrality and sustainable development, including those for renewable energy production, food system transformation, waste valorization, C sink conservation, and C-negative manufacturing. The wealth of knowledge disseminated in this review could inspire the global community and drive the further development of innovative technologies to mitigate climate change and sustainably support human activities.

Fabrication of More Oxygen Vacancies and Depression of Encapsulation for Superior Catalysis in the Water-Gas Shift Reaction.

Fabrication of sufficient oxygen vacancies and exposure of active sites to reactants are two key factors to obtain high catalytic activity in the water-gas shift (WGS) reaction. However, these two factors are hard to satisfy spontaneously, since the formation of oxygen vacancies and encapsulation of metal nanoparticles are two inherent properties in reducible metal oxide supported catalysts due to the strong metal-support interaction (SMSI) effect. In this work, we find that addition of alkali to an anatase supported Ni catalyst (Ni/TiO2(A)) could well regulate the SMSI to achieve both more oxygen vacancies and depression of encapsulation; therefore, more than 20-fold enhancement in activity is obtained. It is found that the in situ formed titanate species on the catalyst surface is crucial to the formation of oxygen vacancies and depression of encapsulation. Furthermore, the methanation, a common side reaction of the WGS reaction, is successfully suppressed in the whole catalytic process.

Can nitrogen-based complex hydrides be a hydrogen isotope separation material?

A nitrogen-based complex hydride is investigated for hydrogen isotope separation for the first time. The experimental results show that a lithium amide-lithium hydride composite (Li-N-H) possesses a distinct positive isotope effect with a separation factor of 1.42. The H-D exchange process in this system occurs at 373 K and can be accelerated with the increase of temperature.

In situ formed Co from a Co-Mg-O solid solution synergizing with LiH for efficient ammonia synthesis.

A cobalt magnesium oxide solid solution (Co-Mg-O) supported LiH catalyst has been synthesized, in which LiH functions both as a strong reductant for the in situ formation of Co metal nanoparticles and a key active component for ammonia synthesis catalysis. Dispersion of the Co-LiH composite on the Co-Mg-O support results in a significantly higher ammonia synthesis rate under mild reaction conditions (19 mmol g-1 h-1 at 300 °C, 10 bar).

In situ synchrotron radiation investigation of V2O5-Nb2O5 metastable compounds: transformational kinetics at high temperatures with a new structural solution for the orthorhombic V4Nb20O60 phase.

Due to the considerable interest in vanadium niobium oxides as a lithium storage material, the kinetics and transformation processes of the V2O5-5Nb2O5 system have been investigated by in situ synchrotron powder X-ray diffraction. The diffraction data after the thermal treatments selected with a view on the most significant features were supplemented with specific ex situ experiments conducted using a laboratory rotating anode X-ray diffractometer. The morphological changes of the mixed powders assuming an amorphous and nanocrystalline solid solution structure as a function of the temperature were inspected by scanning electron microscopy observations. The structural solution of the powder diffraction pattern of the phase recorded in situ at a temperature of about 700 °C was compatible with an orthorhombic crystal structure with the space group Amm2. The obtained lattice parameters for this structure were a = 3.965 Å; b = 17.395 Å, c = 17.742 Å, and the cell composition was V4Nb20O60, Pearson symbol oA84, and density = 4.10 g cm-3. In this structure, while the niobium atoms may be four-, five-, and six-fold coordinated by oxygen atoms, the vanadium atoms were six-fold or seven-fold coordinated. At the temperature of 800 °C and just above, the selected 1 : 2 and 1 : 3 V2O5-Nb2O5 compositions, respectively, returned mostly a tetragonal VNb9O25 phase, in line with earlier observations conducted for determination of the stability phase diagram of such quasi-binary systems.

Complex Hydrides for Energy Storage, Conversion, and Utilization.

Functional materials are the key enabling factor in the development of clean energy technologies. Materials of particular interest, which are reviewed herein, are a class of hydrogenous compound having the general formula of M(XHn )m , where M is usually a metal cation and X can be Al, B, C, N, O, transition metal (TM), or a mixture of them, which sets up an iono-covalent or covalent bonding with H. M(XHn )m is generally termed as a complex hydride by the hydrogen storage community. The rich chemistry between H and B/C/N/O/Al/TM allows complex hydrides of diverse composition and electronic configuration, and thus tunable physical and chemical properties, for applications in hydrogen storage, thermal energy storage, ion conduction in electrochemical devices, and catalysis in fuel processing. The recent progress is reviewed here and strategic approaches for the design and optimization of complex hydrides for the abovementioned applications are highlighted.

Insights into the Rb-Mg-N-H System: an Ordered Mixed Amide/Imide Phase and a Disordered Amide/Hydride Solid Solution.

The crystal structure of a mixed amide-imide phase, RbMgND2ND, has been solved in the orthorhombic space group Pnma ( a = 9.55256(31), b = 3.70772(11) and c = 10.08308(32) Å). A new metal amide-hydride solid solution, Rb(NH2) xH(1- x), has been isolated and characterized in the entire compositional range. The profound analogies, as well as the subtle differences, with the crystal chemistry of KMgND2ND and K(NH2) xH1- x are thoroughly discussed. This approach suggests that the comparable performances obtained using K- and Rb-based additives for the Mg(NH2)2- 2LiH and 2LiN H2-MgH2 hydrogen storage systems are likely to depend on the structural similarities of possible reaction products and intermediates.

Li2 NH-LiBH4 : a Complex Hydride with Near Ambient Hydrogen Adsorption and Fast Lithium Ion Conduction.

Complex hydrides have played important roles in energy storage area. Here a complex hydride made of Li2 NH and LiBH4 was synthesized, which has a structure tentatively indexed using an orthorhombic cell with a space group of Pna21 and lattice parameters of a=10.121, b=6.997, and c=11.457 Å. The Li2 NH-LiBH4 sample (in a molar ratio of 1:1) shows excellent hydrogenation kinetics, starting to absorb H2 at 310 K, which is more than 100 K lower than that of pristine Li2 NH. Furthermore, the Li+ ion conductivity of the Li2 NH-LiBH4 sample is about 1.0×10-5  S cm-1 at room temperature, and is higher than that of either Li2 NH or LiBH4 at 373 K. Those unique properties of the Li2 NH-LiBH4 complex render it a promising candidate for hydrogen storage and Li ion conduction.

Kinetic alteration of the 6Mg(NH2)2-9LiH-LiBH4 system by co-adding YCl3 and Li3N.

The 6Mg(NH2)2-9LiH-LiBH4 composite system has a maximum reversible hydrogen content of 4.2 wt% and a predicted dehydrogenation temperature of about 64 °C at 1 bar of H2. However, the existence of severe kinetic barriers precludes the occurrence of de/re-hydrogenation processes at such a low temperature (H. Cao, G. Wu, Y. Zhang, Z. Xiong, J. Qiu and P. Chen, J. Mater. Chem. A, 2014, 2, 15816-15822). In this work, Li3N and YCl3 have been chosen as co-additives for this system. These additives increase the hydrogen storage capacity and hasten the de/re-hydrogenation kinetics: a hydrogen uptake of 4.2 wt% of H2 was achieved in only 8 min under isothermal conditions at 180 °C and 85 bar of H2 pressure. The re-hydrogenation temperature, necessary for a complete absorption process, can be lowered below 90 °C by increasing the H2 pressure above 185 bar. Moreover, the results indicate that the hydrogenation capacity and absorption kinetics can be maintained roughly constant over several cycles. Low operating temperatures, together with fast absorption kinetics and good reversibility, make this system a promising on-board hydrogen storage material. The reasons for the improved de/re-hydrogenation properties are thoroughly investigated and discussed.

Transition and Alkali Metal Complex Ternary Amides for Ammonia Synthesis and Decomposition.

A new complex ternary amide, Rb2 [Mn(NH2 )4 ], which simultaneously contains both transition and alkali metal catalytic sites, is developed. This is in line with the recently reported TM-LiH composite catalysts, which have been shown to effectively break the scaling relations and achieve ammonia synthesis under mild conditions. Rb2 [Mn(NH2 )4 ] can be facilely synthesized by mechanochemical reaction at room temperature. It exhibits two temperature-dependent polymorphs, that is, a low-temperature orthorhombic and a high-temperature monoclinic structure. Rb2 [Mn(NH2 )4 ] decomposes to N2 , H2 , NH3 , Mn3 N2 , and RbNH2 under inert atmosphere; whereas it releases NH3 at a temperature as low as 80 °C under H2 atmosphere. Those unique behaviors enable Rb2 [Mn(NH2 )4 ], and its analogue K2 [Mn(NH2 )4 ], to be excellent catalytic materials for ammonia decomposition and synthesis. Experimental results show both ammonia decomposition onset temperatures and conversion rates over Rb2 [Mn(NH2 )4 ] and K2 [Mn(NH2 )4 ] are similar to those of noble metal Ru-based catalysts. More importantly, these ternary amides exhibit superior capabilities in catalyzing NH3 synthesis, which are more than 3 orders of magnitude higher than that of Mn nitride and twice of that of Ru/MgO. The in situ SR-PXD measurement shows that manganese nitride, synergistic with Rb/KH or Rb/K(NH2 )x H1-x , are likely the active sites. The chemistry of Rb2 /K2 [Mn(NH2 )x ] and Rb/K(NH2 )x H1-x with H2 /N2 and NH3 correlates closely with the catalytic performance.

Effects of Stoichiometry on the H2 -Storage Properties of Mg(NH2 )2 -LiH-LiBH4 Tri-Component Systems.

The hydrogen desorption pathways and storage properties of 2 Mg(NH2 )2 -3 LiH-xLiBH4 samples (x=0, 1, 2, and 4) were investigated systematically by a combination of pressure composition isotherm (PCI), differential scanning calorimetric (DSC), and volumetric release methods. Experimental results showed that the desorption peak temperatures of 2 Mg(NH2 )2 -3 LiH-xLiBH4 samples were approximately 10-15 °C lower than that of 2 Mg(NH2 )2 -3 LiH. The 2 Mg(NH2 )2 -3 LiH-4 LiBH4 composite in particular began to release hydrogen at 90 °C, thereby exhibiting superior dehydrogenation performance. All of the LiBH4 -doped samples could be fully dehydrogenated and re-hydrogenated at a temperature of 143 °C. The high hydrogen pressure region (above 50 bar) of PCI curves for the LiBH4 -doped samples rose as the amount of LiBH4 increased. LiBH4 changed the desorption pathway of the 2 Mg(NH2 )2 -3 LiH sample under a hydrogen pressure of 50 bar, thereby resulting in the formation of MgNH and molten [LiNH2 -2 LiBH4 ]. That is different from the dehydrogenation pathway of 2 Mg(NH2 )2 -3 LiH sample without LiBH4 , which formed Li2 Mg2 N3 H3 and LiNH2 , as reported previously. In addition, the results of DSC analyses showed that the doped samples exhibited two independent endothermic events, which might be related to two different desorption pathways.

The effect of Sr(OH)2 on the hydrogen storage properties of the Mg(NH2)2-2LiH system.

The doping effect of Sr(OH)2 on the Mg(NH2)2-2LiH system is investigated considering different amounts of added Sr(OH)2 in the range of 0.05 to 0.2 mol. Experimental results show that both the thermodynamic and the kinetic properties of Mg(NH2)2-2LiH are influenced by the presence of Sr(OH)2. The addition of 0.1 mol Sr(OH)2 leads to a decrease in both the dehydrogenation onset and peak temperatures of ca. 70 and 13 °C, respectively, and an acceleration in the de/re-hydrogenation rates of one time at 150 °C compared to Mg(NH2)2-2LiH alone. Based on differential scanning calorimetry (DSC) analysis, the overall reaction enthalpy of the 0.1 Sr(OH)2-doped sample is calculated to be 44 kJ per mol-H2 and there are two absorption events occurring in the doped sample instead of one in the pristine sample. For the applied experimental conditions, according to the in situ synchrotron radiation powder X-ray diffraction (SR-PXD) and Fourier Transform Infrared spectroscopy (FT-IR) analysis, the reaction mechanism has been finally defined: Sr(OH)2, Mg(NH2)2 and LiH react with each other to form SrO, MgO and LiNH2 during ball milling. After heating, SrO interacts with Mg(NH2)2 producing MgO and Sr(NH2)2. Then Mg(NH2)2, LiNH2 and Sr(NH2)2 react with LiH to produce Li2NH, SrNH, Li2Mg(NH)2 and Li2Mg2(NH)3 in traces. After re-hydrogenation, LiSrH3, LiH and LiNH2 are formed along with amorphous Mg(NH2)2. The reasons for the improved kinetics are: (a) during dehydrogenation, the in situ formation of SrNH appears to increase the interfacial contacts between Mg(NH2)2 and LiH and also weakens the N-H bond of Mg(NH2)2; (b) during absorption, the formation of LiSrH3 at around 150 °C could be the key factor for improving the hydrogenation properties.

KNH2-KH: a metal amide-hydride solid solution.

We report for the first time the formation of a metal amide-hydride solid solution. The dissolution of KH into KNH2 leads to an anionic substitution, which decreases the interaction among NH2- ions. The rotational properties of the high temperature polymorphs of KNH2 are thereby retained down to room temperature.

New synthesis route for ternary transition metal amides as well as ultrafast amide-hydride hydrogen storage materials.

K2[Mn(NH2)4] and K2[Zn(NH2)4] were successfully synthesized via a mechanochemical method. The mixture of K2[Mn(NH2)4] and LiH showed excellent rehydrogenation properties. In fact, after dehydrogenation K2[Mn(NH2)4]-8LiH fully rehydrogenates within 60 seconds at ca. 230 °C and 5 MPa of H2. This is one of the fastest rehydrogenation rates in amide-hydride systems known to date. This work also shows a strategy for the synthesis of transition metal nitrides by decomposition of the mixtures of M[M'(NH2)n] (where M is an alkali or alkaline earth metal and M' is a transition metal) and metal hydrides.

Ternary Amides Containing Transition Metals for Hydrogen Storage: A Case Study with Alkali Metal Amidozincates.

The alkali metal amidozincates Li4 [Zn(NH2)4](NH2)2 and K2[Zn(NH2)4] were, to the best of our knowledge, studied for the first time as hydrogen storage media. Compared with the LiNH2-2 LiH system, both Li4 [Zn(NH2)4](NH2)2-12 LiH and K2[Zn(NH2)4]-8 LiH systems showed improved rehydrogenation performance, especially K2[Zn(NH2)4]-8 LiH, which can be fully hydrogenated within 30 s at approximately 230 °C. The absorption properties are stable upon cycling. This work shows that ternary amides containing transition metals have great potential as hydrogen storage materials.