Article
Engineering, Environmental
Yongyang Zhu, Shaoyang Shen, Liuzhang Ouyang, Jiangwen Liu, Hui Wang, Zhenguo Huang, Min Zhu
Summary: This study reports an economical method to synthesize Mg(BH4)(2) by converting B-O bonds in widely available borates or boric acid to B-H. This method avoids expensive boron sources and high pressure and temperature conditions, significantly reducing costs, and could be an alternative to the current synthesis processes of Mg(BH4)(2).
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Noemi Leick, Ba L. Tran, Mark E. Bowden, Thomas Gennett, Tom Autrey
Summary: This study investigated the thermal stability of coordination complexes formed between different glymes with Mg(BH4)(2), revealing diverse phase transitions, speciations, and decomposition pathways despite their structural similarities.
DALTON TRANSACTIONS
(2022)
Review
Crystallography
Nuraini Ruslan, Muhammad Syarifuddin Yahya, Md Nurul Islam Siddique, Ashish Prabhakar Yengantiwar, Mohammad Ismail, Md Rabiul Awal, Mohd Zaki Mohd Yusoff, Muhammad Firdaus Asyraf Abdul Halim Yap, Nurul Shafikah Mustafa
Summary: Metal hydrides such as MgH2 and NaBH4 have high potential for solid-state hydrogen storage. However, a dehydrogenation process is required prior to hydrogen utilization. The hydrolysis method is a possible way to extract or generate hydrogen, but issues like passivation layer, high cost and sluggish self-hydrolysis can be overcome with the help of catalysts. Studies have shown that adding catalysts like chloride, oxide, fluoride, platinum, ruthenium, cobalt, and nickel can significantly enhance the amount of hydrogen released during the hydrolysis of MgH2 and NaBH4.
Article
Chemistry, Physical
Hui Luo, Yunshu Yang, Liwen Lu, Guangxu Li, Xinhua Wang, Xiantun Huang, Xiaoma Tao, Cunke Huang, Zhiqiang Lan, Wenzheng Zhou, Jin Guo, Haizhen Liu
Summary: In this study, a two-dimensional Ti3CN MXene was synthesized and added to the Li-Mg-B-H composite, resulting in a reduction in the dehydrogenation temperature and induction period of the composite. The reversible capacity and capacity retention ratio of the composite were maintained at high levels. Micro-structure studies revealed the transformation of Ti3CN into highly-dispersed nano-TiB2, which acted as an active catalyst to improve the kinetics and reversibility of the composite. This research provides insights into the role of MXene in tailoring the hydrogen storage properties of metal borohydride-based composites.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Zi Jun Gao, Zhou Peng Li, Bin Hong Liu
Summary: In this study, La-incorporated Ni-B amorphous composites were synthesized and found to significantly improve the dehydrogenation kinetics of MgH2, showing higher structural and catalytic stability.
JOURNAL OF ALLOYS AND COMPOUNDS
(2021)
Article
Energy & Fuels
N. S. C. Mazlan, F. A. Halim Yap, M. S. Yahya, S. B. Mohamed, N. A. Sazelee, N. A. Ali, I. Jusoh, M. Ismail
Summary: This study focuses on the catalytic effect of TiF3 on the hydrogen storage properties of the MgH2-Na3AlH6-LiBH4 system produced by ball milling. The addition of TiF3 catalyst results in a faster hydrogen uptake and release rate compared to the catalyst-free system. The apparent activation energy for the dissociation of Li3AlH6, MgH2, and NaBH4 in the TiF3-doped composite is significantly reduced. TiF3's catalytic performance is attributed to the in-situ production of Al-Ti and Al-F phases during the dehydrogenation process.
JOURNAL OF ENERGY STORAGE
(2023)
Article
Chemistry, Physical
Shuhua Zhou, Wei Zhang, Wenfeng Wang, Yaokun Fu, Han Yu, Lu Zhang, Jianzheng Song, Ying Cheng, Shumin Han
Summary: A novel method involving cosintering of an organic material, pure Mg, and a hydriding combustion synthesis technique has been reported to prepare MgH2 with amorphous carbon, resulting in significantly improved dehydrogenation capacity and kinetics compared to pure MgH2.
ACS APPLIED ENERGY MATERIALS
(2021)
Article
Engineering, Environmental
Ren Zou, Joshua Adedeji Bolarin, Gangtie Lei, Wenbo Gao, Zhi Li, Hujun Cao, Ping Chen
Summary: This work aims to investigate the dehydrogenation behavior and chemical state changes of a MgH2-TiO2 composite under microwave irradiation. It is found that reduced titanium oxide formed during ball milling can absorb microwave radiation and act as hot spots, resulting in significant dehydrogenation of the MgH2 sample. Furthermore, microwave irradiation promotes the reduction of Ti4+ and facilitates electron transfer between Mg2+ and H- for improved hydrogen sorption.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Energy & Fuels
Rashmi Dahal, Jenny G. Vitillo, Anna C. Asland, Christoph Frommen, Stefano Deledda, Olena Zavorotynska
Summary: Magnesium borohydride (Mg(BH4)(2)) is a solid-state hydrogen storage compound that has high hydrogen densities and low operational temperature. This study used spectroscopic methods to investigate the reaction intermediates and provided additional insights into this decomposition reaction.
Article
Chemistry, Multidisciplinary
Anna Zabilska, Maxim Zabilskiy, Rob Jeremiah G. Nuguid, Adam H. H. Clark, Ilia I. I. Sadykov, Maarten Nachtegaal, Oliver Kroecher, Olga V. V. Safonova
Summary: In this study, the origin of the volcano-shaped activity trend for VOx/CeOx catalysts in ethanol oxidative dehydrogenation (ODH) was clarified using operando quick V K- and Ce L-3- edge XAS experiments. It was found that both vanadium and cerium synergistically contribute to the alcohol ODH activity, with the concentration of reversible Ce4+/Ce3+ species being the main descriptor. The activity drop observed at a surface loading above ca. 3 V nm(-2) (ca. 30% VOx monolayer coverage) was attributed to the formation of spectator V4+ and Ce3+ species, which were identified for the first time.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Yuting Shao, Haiguang Gao, Qinke Tang, Yana Liu, Jiangchuan Liu, Yunfeng Zhu, Jiguang Zhang, Liquan Li, Xiaohui Hu, Zhixin Ba
Summary: Three-dimensionally ordered macroporous (3DOM) TiO2, prepared by colloidal crystal template method, can enhance the hydrogen storage properties of MgH2 by providing numerous reactive sites for hydrogen de/absorption. The electron transfer on contact interface between MgH2 and TiO2 plays a crucial role in promoting dehydrogenation. This finding is of great significance for developing highly efficient catalysts based on 3DOM structure in hydrogen storage materials.
APPLIED SURFACE SCIENCE
(2022)
Review
Materials Science, Multidisciplinary
Joshua Adedeji Bolarin, Ren Zou, Zhi Li, Zhao Zhang, Hujun Cao
Summary: This article discusses the importance of hydrogen fuel as an alternative source of renewable energy and the development of solid-state hydrogen storage in magnesium hydride (MgH2). It highlights the temperature requirement and slow kinetics of MgH2 as barriers to its wide commercial applications. The article also explores nanostructuring and catalysis as promising strategies for modifying the properties of MgH2. Additionally, it provides insights into the recent applications of MXenes, a group of 2D nanomaterials, in hydrogen storage and enhancing the hydrogen reactions of MgH2.
APPLIED MATERIALS TODAY
(2022)
Article
Metallurgy & Metallurgical Engineering
Jian Zhang, Shuai Yan, Guanglin Xia, Xiaojie Zhou, Xianzheng Lu, Linping Yu, Xuebin Yu, Ping Peng
Summary: This study confirms that doping low-valence transition metals into MgO can weaken Mg-H bonds and reduce energy required for hydrogen desorption, resulting in superior catalytic activity compared to TMOs and MgO. The hybridization between Mg(Nb)O and MgH2 promotes charge transfer, enhancing hydrogen storage performance with reduced activation energy and increased reversible capacity.
JOURNAL OF MAGNESIUM AND ALLOYS
(2021)
Article
Materials Science, Multidisciplinary
Hu Yao, Guang Zeng, Qinfen Gu, Kazuhiro Nogita, Jing Guo, Qian Li
Summary: The influences of microstructure evolution induced by thermal-mechanical processing on the hydrogen storage performance of Mg-Ni-Gd-Y-Zn-Cu alloys were investigated. The extruded alloy showed higher hydrogen absorption capacity and faster hydrogen ab/desorption kinetics due to refined alpha-Mg grains and the presence of 14H-type LPSO phases. These findings have implications for the design and manufacturing of magnesium-based hydrogen storage materials.
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Han Yu, Ying Cheng, Yaokun Fu, Lu Zhang, Sanyang Guo, Yuan Li, Wei Zhang, Shumin Han
Summary: In this study, a facile method was used to cover MgH2 with amorphous carbon formed in situ, resulting in the MgH2-CPF composite material. This material exhibited higher dehydrogenation rate and absorption capacity at lower temperatures, and the addition of carbon layer reduced the apparent activation energy of the reaction.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Inorganic & Nuclear
Igor E. E. Golub, Michael Heere, Volodia Gounaris, Xiao Li, Timothy Steenhaut, Jian Wang, Koen Robeyns, Hai-Wen Li, Iurii Dovgaliuk, Kazutaka Ikeda, Geoffroy Hautier, Yaroslav Filinchuk
Summary: The highly complex crystal structure of stoichiometric Mg-5(en)(6)(BH4)(10) was determined using single crystal synchrotron X-ray diffraction and confirmed by neutron powder diffraction on isotopically substituted Mg(en)(1.2)((BD4)-B-11)(2). The role of amorphous Mg(BH4)(2) in the reactivity of the Mg(BH4)(2)-en system was emphasized, and a previously overlooked phase, Mg(en)(2)(BH4)(2), was characterized.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jian Wang, Timothy Steenhaut, Hai-Wen Li, Yaroslav Filinchuk
Summary: A simple, efficient, and environmentally friendly solvothermal method was developed to prepare high-purity Na2B12H12 and K2B12H12, paving the way for large-scale synthesis of M(x)B(12)H(12) derivatives.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Rama Srinivas Varanasi, Motomichi Koyama, Hiroyuki Saitoh, Reina Utsumi, Toyoto Sato, Shin-ichi Orimo, Eiji Akiyama
Summary: The phase transformations and microstructure changes during the depressurization of non-hydrogenated and hydrogenated Fe-Mn-Si-Cr alloy were investigated. Understanding the effects of hydrogenation on the stability of the austenite phase in Fe-based alloys is crucial.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Physical
Gaspar Andrade, Guilherme Zepon, Kaveh Edalati, Abbas Mohammadi, Zhongliang Ma, Hai-Wen Li, Ricardo Floriano
Summary: The crystal structure and hydrogen storage properties of a new equiatomic TiZrNbCrFeNi high-entropy alloy (HEA) were investigated. The alloy exhibited an AB-type configuration, selected through thermodynamic calculations and showed the ability to absorb 1.5 wt% of hydrogen at room temperature without activation. Cyclical testing revealed changes in the fractions of two C14 Laves phases, with one phase having higher reactivity towards hydrogen. The alloy exhibited a single C14 Laves phase after dehydrogenation at 473 K, and microstructural analysis showed excellent homogeneity and element distribution.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Chemistry, Physical
Ryuhei Sato, Kazuto Akagi, Shigeyuki Takagi, Kartik Sau, Kazuaki Kisu, Hao Li, Shin-ichi Orimo
Summary: Topological data analysis based on persistent homology is applied to the molecular dynamics simulation of the AgI a-phase to analyze the ion migration mechanism effectively. The persistence diagrams of a-AgI record the shape and size of the ring structures in the atomic configurations, clearly showing the emergence of four-membered rings formed by two Ag and two I ions at high temperatures, which are common structures during the Ag ion migration. The potential energy change due to the deformation of the four-membered ring agrees well with the activation energy calculated from the conductivity Arrhenius plot, and the concerted motion of two Ag ions via the four-membered ring is successfully extracted from molecular dynamics simulations, providing new insight into the specific mechanism of the concerted motion.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Kohei Inagawa, Daiju Matsumura, Masashi Taniguchi, Shinya Uegaki, Tomohito Nakayama, Junnosuke Urano, Takuro Aotani, Hirohisa Tanaka
Summary: Passive autocatalytic recombiner (PAR) is a potential technology for ensuring process safety in the hydrogen society by catalytically oxidizing hydrogen to water, effectively mitigating the risk of explosions. CO is a catalyst poison that hampers catalytic reactions. In situ and time-resolved X-ray absorption spectroscopy analyses revealed that the Pt-Fe/CZY catalyst exhibited notable hydrogen oxidation activity even in the presence of CO, attributed to the combined effects of Pt-Fe alloy composition and CZY support materials.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Katsuaki Sugawara, Haruki Kusaka, Tappei Kawakami, Koki Yanagizawa, Asuka Honma, Seigo Souma, Kosuke Nakayama, Masashi Miyakawa, Takashi Taniguchi, Miho Kitamura, Koji Horiba, Hiroshi Kumigashira, Takashi Takahashi, Shin-ichi Orimo, Masayuki Toyoda, Susumu Saito, Takahiro Kondo, Takafumi Sato
Summary: Boron-based two-dimensional materials, especially rhombohedral boron monosulfide (r-BS), with its unique layered crystal structure, are being extensively studied for their potential applications in nanoelectronics. However, the analysis of the fundamental electronic properties of r-BS has been limited due to the lack of available large crystals. In this study, we utilize microfocused angle-resolved photoemission spectroscopy (micro-ARPES) to directly map the band structure of a tiny r-BS powder crystal, revealing that r-BS is a p-type semiconductor with an anisotropic in-plane effective mass and a band gap larger than 0.5 eV. These findings demonstrate the high applicability of micro-ARPES for investigating small powder crystals and provide new insights into the unexplored electronic states of novel materials.
Article
Chemistry, Inorganic & Nuclear
Zhi-Kang Qin, Li-Qing He, Xiao-Li Ding, Ting-Zhi Si, Ping Cui, Hai-Wen Li, Yong-Tao Li
Summary: Building liquid channels in magnesium hydride by introducing lithium borohydride ion conductors improves its low-temperature hydrogen sorption. For example, 5 wt% LiBH4-doped MgH2 can release about 7.1 wt.% H-2 within 40 min at 300 degrees C, while pure MgH2 only desorbs less than 0.7 wt.% H-2. Additionally, the LiBH4-doped MgH2 exhibits faster desorption kinetics with more than 10 times enhancement compared to pure MgH2, and maintains a stable cyclic performance even after six absorption and desorption cycles. This approach provides insights for promoting hydrogen absorption and desorption of other metal hydrides.
Article
Chemistry, Physical
Egon Campos dos Santos, Ryuhei Sato, Kazuaki Kisu, Kartik Sau, Xue Jia, Fangling Yang, Shin-ichi Orimo, Hao Li
Summary: The need for next-generation batteries is urgent. Divalent closo-type complex hydride (CTCH) electrolytes have been shown to offer valuable alternatives to lithium-ion technology. However, the complex structure of neutral molecules containing CTCHs poses challenges for understanding ionic diffusion mechanisms and designing high-performance batteries. This study combines a genetic algorithm and ab initio simulations to analyze cation diffusions in various CTCHs, leading to the development of structure-performance relationships and paving the way for precise modeling of complex materials.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
V. Charbonnier, R. Utsumi, Y. Nakahira, H. Enoki, K. Asano, H. Kim, T. Sato, S. Orimo, H. Saitoh, K. Sakaki
Summary: For high pressure MH compressor applications, it is important to understand the hydrogenation properties of MH forming compounds under high pressure and temperature conditions, which are still little studied. This study investigated a Ti0.90V0.30Mn1.00Ni0.80 compound with an AB2 structure using Sieverts' method, providing experimental evidence of the non-ideal behavior of hydrogen in the high-pressure region. The study also demonstrated the estimation of high-sorption pressures using low-pressure data and monitored the structural evolution of the compound under ultra-high hydrogen pressure.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Review
Chemistry, Physical
Junrui Zhang, Haiwen Li, Xuezhang Xiao, Liuzhang Ouyang
Summary: Metal borohydrides have high theoretical hydrogen production/storage densities and offer efficient real-time hydrogen supply for electronics. However, their practical applications are limited. Strategies to overcome these limitations, such as optimizing the boron/hydrogen source and reducing agent, are summarized in this review. Ouyang developed a practical and low-cost method for regenerating MBH4 by ball milling, which has the potential to decrease the synthesis cost and increase the reversibility of metal borohydrides.
JOURNAL OF ALLOYS AND COMPOUNDS
(2023)
Article
Materials Science, Multidisciplinary
Shunqin Zeng, Xiaoli Ding, Liqing He, Hai-Wen Li, Qingan Zhang, Yongtao Li
Summary: Dual lithium-containing hydride/oxide shells are formed by in situ mechano-induced assembly of Li3PO4 and LiBH4. The ionic conductivity of the Li3PO4-based composite is significantly improved by nearly 4 orders of magnitude, reaching 0.04 mS cm(-2) at 75°C, with an electrochemical window of -0.2-5 V (vs. Li/Li+).
MATERIALS ADVANCES
(2023)
Article
Materials Science, Multidisciplinary
Kartik Sau, Shigeyuki Takagi, Tamio Ikeshoji, Kazuaki Kisu, Ryuhei Sato, Shin-ichi Orimo
Summary: Using molecular dynamics (MD) simulations, we investigated the effect of cation size on the ordered-disordered phase-transition temperature (T-tran) and cationic diffusion in the complex hydride LiCB11H12. The results showed that introducing a large-size cation with high cell volume can lower T-tran by facilitating anionic rotation. The study also provided insights into cationic density distribution, bottlenecks in the cationic path, and the hopping mechanism with increasing cationic sizes.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Physical
Fuhu Yin, Yu Chang, Tingzhi Si, Jing Chen, Hai-Wen Li, Yongtao Li, Qingan Zhang
Summary: In this study, new Zr-based high-entropy alloys with Laves phases were designed, and their structure and hydrogen storage properties were adjusted by introducing Mg element. The results show that the addition of Mg element improves the hydrogen storage capacity and kinetics of these alloys, making them potential candidates for hydrogen storage materials.
Article
Chemistry, Inorganic & Nuclear
Bingjie Ma, Wenbin Jiang, Liuzhang Ouyang, Haiwen Li
Summary: This study suggests using glycine as an electrolyte additive in 3.5 wt% NaCl solution to enhance the discharge performance of commercial AZ31 magnesium alloys at high current densities.
INORGANIC CHEMISTRY FRONTIERS
(2023)
