Ruthenium Complex Hydride Catalysts as a Platform for Ammonia Synthesis

Mild-condition ammonia synthesis from N2 and H2 is a long-sought-after scientific goal and a practical need, especially for the intensively pursued “Green Ammonia” production using renewable H2. Under this context, there have been growing interests in the development of new catalysts for effectively catalyzing N2+H2 to NH3. Particular attention has been given to Ru-based catalysts because they are well known to be more active at lower temperatures and pressures than non-noble-metal based catalysts. Here, we demonstrate that a series of Ru complex hydrides An[RuHm], where A is alkali or alkaline earth metal, n= 2, 3 or 4 and m = 6 or 7, exhibit universal and high catalytic activities that far exceed the benchmark Ru metal catalysts under mild conditions. Detailed investigations on the ternary Ru complex hydride catalytic system disclose that the kinetic behaviors depend strongly on the identity of alkali or alkaline earth metal cations. In clear contrast to the closed packed Ru metal catalyst, the unique configuration and synergized scenario of the Ru complex hydride center prefer a non-dissociative mechanism for N2 activation and hydrogenation, which provides a new platform for the design and development of efficient NH3 synthesis catalysts.

Ruthenium Complex Hydride Catalysts as a Platform for Ammonia Synthesis

Mild-condition ammonia synthesis from N2 and H2 is a long-sought-after scientific goal and a practical need, especially for the intensively pursued “Green Ammonia” production using renewable H2. Under this context, there have been growing interests in the development of new catalysts for effectively catalyzing N2+H2 to NH3. Particular attention has been given to Ru-based catalysts because they are well known to be more active at lower temperatures and pressures than non-noble-metal based catalysts. Here, we demonstrate that a series of Ru complex hydrides An[RuHm], where A is alkali or alkaline earth metal, n= 2, 3 or 4 and m = 6 or 7, exhibit universal and high catalytic activities that far exceed the benchmark Ru metal catalysts under mild conditions. Detailed investigations on the ternary Ru complex hydride catalytic system disclose that the kinetic behaviors depend strongly on the identity of alkali or alkaline earth metal cations. In clear contrast to the closed packed Ru metal catalyst, the unique configuration and synergized scenario of the Ru complex hydride center prefer a non-dissociative mechanism for N2 activation and hydrogenation, which provides a new platform for the design and development of efficient NH3 synthesis catalysts.

Influence of Synthesis Gas Components on Hydrogen Storage Properties of Sodium Aluminum Hexahydride

A systematic study of different ratios of CO, CO2, N2 gas components on the hydrogen storage properties of the Na3AlH6 complex hydride with 4 mol% TiCl3, 8 mol% aluminum and 8 mol% activated carbon is presented in this paper. The different concentrations of CO and CO2 in H2 and CO, CO2, N2 in H2 mixture were investigated. Both CO and CO2 gas react with the complex hydride forming Al oxy-compounds, NaOH and Na2CO3 that consequently cause serious decline in hydrogen storage capacity. These reactions lead to irreversible damage of complex hydride under the current experimental condition. Thus, after 10 cycles with 0.1 vol % CO + 99.9 vol %H2 and 1 vol % CO + 99 vol %H2, the dehydrogenation storage capacity of the composite material decreased by 17.2% and 57.3%, respectively. In the case of investigation of 10 cycles with 1 vol % CO2 + 99 vol % H2 gas mixture, the capacity degradation was 53.5%. After 2 cycles with 10 vol % CO +90 vol % H2, full degradation was observed, whereas after 6 cycles with 10 vol % CO2 + 90 vol % H2, degradation of 86.8% was measured. While testing with the gas mixture of 1.5 vol % CO + 10 vol % CO2 + 27 vol % H2 + 61.5 vol % N2, the degradation of 94% after 6 cycles was shown. According to these results, it must be concluded that complex aluminum hydrides cannot be used for the absorption of hydrogen from syngas mixtures without thorough purification.

Hydrogen generation by hydrolysis of metals and hydrides for portable energy supply

NATO project G 5233 “Portable energy supply” was executed by 4 teams (Institute for Energy Technology, Norway and 3 Institutes of the National Academy of Sciences of Ukraine). G5233 Project was focused on the development of hydrogen fueled portable energy supply systems integrating hydrogen generation and storage units based on use of light metals, metal and complex hydride materials and portable fuel cells. The weight efficient energy supply device was developed by using these selected materials and performance-optimised NaBH4 complex hydride. Besides, various new relevant units of equipment for the samples preparation and characterization were ordered and accommodated in the participants labs and the program of training of young scientists at IFE, Norway was accomplished. Different types of materials for hydrogen generation were synthesized and characterized (activated aluminium alloys, Mg-Al alloys, MgH2 and their composites, NaBH4 with catalytic additives). The challenging objective of reaching a completeness of the hydrolysis of MgH2 was achieved; the reaction conditions were optimized and the particular focus applications integrating efficient hydrogen generation systems were identified. The mechanism and the kinetics model of the hydrolysis process of MgH2 in water solutions have been proposed which successfully describe the experimental data. In parallel with the hydrolysis reaction resulting in hydrogen generation and formation of Mg(OH)2 , the process involves passivation of the MgH2 surface by the formed Mg(OH)2 precipitate followed by its re-passivation with the rate constants of these processes being established. Increase of the concentration of MgCl2 leads to just a minor increase in the rate constant of the interaction of MgH2 with water but leads to a sharp increase of the rate constant of the repassivation of MgH2 surface. To achieve efficient hydrolysis of NaBH4 , different types of catalysts (heterogeneous on the basis of Pt and "homogeneous" - salts of Ni+2 and Co+2) were studied and optimized. Several systems were selected as candidates to provide the required hydrogen flow to operate a 30 W fuel cell over a given time exceeding 1 hour, based on a use of inexpensive and affordable hydrogen-containing materials and catalytic additives. 3 individual hydrolysis workstations (1 in Norway and 2 in Ukraine) were built, tested and optimized. The plan of the work to reach the objectives of the Project G5233 “Portable energy supply” is completely accomplished, all the milestones are successfully fulfilled and the overall goal of the Project is reached.

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

The nitrogen-based complex hydride Li–N–H has positive thermodynamic isotope effects with a separation factor of 1.42.