Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N–C for Hydrogen Storage in NaAlH<sub>4</sub>

Zhang, Xin; Ren, Zhuanghe; Lu, Yunhao; Yao, Jianhua; Gao, Mingxia; Liu, Yongfeng; Pan, Hongge

doi:10.1021/acsami.8b04011

Cited by 42 publications

(14 citation statements)

References 53 publications

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“…d) Isothermal dehydrogenation of the pristine and 7 wt% TiN@N‐C doped NaAlH 4 at 140 °C, inset is the proposed reaction mechanism. Reproduced with permission . Copyright 2018, American Chemical Society.…”

Section: Hydrogen Storagementioning

confidence: 99%

“…The 7 wt% nano‐Ti@C‐doped NaAlH 4 can hydrogenate completely within 3 min at 100 °C and 120 bar H 2 , moreover, it has a high stability only 0.07 wt% of H 2 is lost after 100 cycles 35b. TiN nanoparticles confined by N‐doped carbon nanorods (nano‐TiN@N‐C) showed superior catalytic activity for de/rehydrogenating NaAlH 4 , i.e., ≈4.9 wt% of H 2 can be released at 140 °C within 60 min, and reabsorbed at 100 °C and 100 bar within 15 min (Figure d) . The abovementioned efforts significantly advance NaAlH 4 for practical applications.…”

Section: Hydrogen Storagementioning

confidence: 99%

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Complex Hydrides for Energy Storage, Conversion, and Utilization

2019

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functionalities and exhibit great potentials for the applications in the energy transfer chain (Figure 1).In chemistry, a hydride is a compound having negatively charged hydrogen anion. [2] Nowadays, however, hydrogenous compounds having hydrogen bonded to metals or nonmetal in ionic, metallic or covalent manner are collectively referred as hydrides. [3] Complex hydride is such a class of compound having a general formula of M(XH n ) m , where M is usually a metal cation and X is a metal or nonmetal element which sets up covalent or ionocovalent bonding with H. [4] The M[XH n ] m is H-rich and can decompose selectively to H 2 allowing complex hydrides of light-weight elements potential hydrogen storage media. As a matter of fact, since the pioneering work of Ti-catalyzed NaAlH 4 in 1997, [5] extensive investigations on hydrogen storage over alanates, [6] amide-hydride composites, [7] borohydrides, [8] amidoboranes [9] as well as metallorganic hydrides [10] were carried out and tremendous progress has been made (Figure 2). [1,4a] The break and setup of XH bonding would be endergonic and exergonic, respectively. The energy input and output in hydrogen desorption and reabsorption over a complex hydride depends strongly on its thermodynamic stability, which also offers an opportunity of using complex hydrides as thermal energy storage materials to cope up with the intermittent, fluctuating and unstable supply of renewable energies. Owning to their exclusive advantages of diversity, high energy densities and tunability, complex hydrides have been actively pursued for this application since year 2000. [11] Solid electrolytes with fast conduction of Li, Na, or Mg ions are highly demanded for all-solid-state batteries with high energy density and safety. Coincidentally, complex hydrides are composed of those cations and a relatively large sized [XH n ] anion. The coordination flexibility of the large anion with alkali or alkaline earth cation would create some favorable structural features, such as defects and/or low-barrier diffusion channels, to facilitate cation migration within the lattice of complex hydrides. [12] Starting from the finding of high Li-ion conduction in the high-temperature-phase LiBH 4 , [13] a variety of complex hydrides has been developed, some of which show superior ion conductivity to their nonhydride peers. [14] Hydrogen storage over complex hydride would undergo dihydrogen dissociation into surface H atoms followed by H 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(XH n ) 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(XH n ) 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 compo...

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Section: Hydrogen Storagementioning

confidence: 99%

Section: Hydrogen Storagementioning

confidence: 99%

Complex Hydrides for Energy Storage, Conversion, and Utilization

2019

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“…In this respect, Bogdanović and Schwickardi contributed an important breakthrough by introducing a few millimoles of Ti(OBu) 4 or TiCl 3 into NaAlH 4 , which enabled reversible hydrogen storage with NaAlH 4 at moderate conditions [15]. After that, a variety of Ti-based species have been explored and evaluated, including halides, oxides, nitrides, borides, carbides, hydrides, alloys, and elemental metals (Figure 1) [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31]. In most cases, the Ti-species tends to react with NaAlH 4 to form Ti x Al y , which shows significant catalytic effect on the de-/rehydrogenation.…”

Section: Introductionmentioning

confidence: 99%

Titanium Hydride Nanoplates Enable 5 wt% of Reversible Hydrogen Storage by Sodium Alanate below 80°C

Ren

Zhang

et al. 2021

Research

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Sodium alanate (NaAlH4) with 5.6 wt% of hydrogen capacity suffers seriously from the sluggish kinetics for reversible hydrogen storage. Ti-based dopants such as TiCl4, TiCl3, TiF3, and TiO2 are prominent in enhancing the dehydrogenation kinetics and hence reducing the operation temperature. The tradeoff, however, is a considerable decrease of the reversible hydrogen capacity, which largely lowers the practical value of NaAlH4. Here, we successfully synthesized a new Ti-dopant, i.e., TiH2 as nanoplates with ~50 nm in lateral size and ~15 nm in thickness by an ultrasound-driven metathesis reaction between TiCl4 and LiH in THF with graphene as supports (denoted as NP-TiH2@G). Doping of 7 wt% NP-TiH2@G enables a full dehydrogenation of NaAlH4 at 80°C and rehydrogenation at 30°C under 100 atm H2 with a reversible hydrogen capacity of 5 wt%, superior to all literature results reported so far. This indicates that nanostructured TiH2 is much more effective than Ti-dopants in improving the hydrogen storage performance of NaAlH4. Our finding not only pushes the practical application of NaAlH4 forward greatly but also opens up new opportunities to tailor the kinetics with the minimal capacity loss.

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“…Recently, it has become a hot issue to construct highly efficient multicomplex dopants or co-dopants with synergetic effects [241,247,[255][256][257][258][259][260][261][262][263]. Bimetallic additives have been explored to promote the hydriding-dehydriding properties of hydrides [256,257].…”

Section: Adding Dopantsmentioning

confidence: 99%

Lightweight hydrides nanocomposites for hydrogen storage: Challenges, progress and prospects

Huang

et al. 2019

Sci. China Mater.

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As typical high-capacity complex hydrides, lightweight hydrides have attracted intensive attention due to their high gravimetric and volumetric energy densities of hydrogen storage. However, lightweight hydrides also have high thermodynamic stability and poor kinetics, so they ususally require high hydrogen desorption temperature and show inferior reversibility under mild conditions. This review summarizes recent progresses on the endeavor of overcoming thermodynamic and kinetic challenges for Mg based hydrides, lightweight metal borohydrides and alanates. First, the current state, advantages and challenges for Mg-based hydrides and lightweight metal hydrides are introduced. Then, alloying, nanoscaling and appropriate doping techniques are demonstrated to decrease the hydrogen desorption temperature and promote the reversibility behavior in lightweight hydrides. Selected scaffolds materials, approaches for synthesis of nanoconfined systems and hydriding-dehydriding properties are reviewed. In addition, the evolution of various dopants and their effects on the hydrogen storage properties of lightweight hydrides are investigated, and the relevant catalytic mechanisms are summarized. Finally, the remaining challenges and the sustainable research efforts are discussed.

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Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N–C for Hydrogen Storage in NaAlH₄

Cited by 42 publications

References 53 publications

Complex Hydrides for Energy Storage, Conversion, and Utilization

Complex Hydrides for Energy Storage, Conversion, and Utilization

Titanium Hydride Nanoplates Enable 5 wt% of Reversible Hydrogen Storage by Sodium Alanate below 80°C

Lightweight hydrides nanocomposites for hydrogen storage: Challenges, progress and prospects

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Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N–C for Hydrogen Storage in NaAlH4

Cited by 42 publications

References 53 publications

Complex Hydrides for Energy Storage, Conversion, and Utilization

Complex Hydrides for Energy Storage, Conversion, and Utilization

Titanium Hydride Nanoplates Enable 5 wt% of Reversible Hydrogen Storage by Sodium Alanate below 80°C

Lightweight hydrides nanocomposites for hydrogen storage: Challenges, progress and prospects

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Facile Synthesis and Superior Catalytic Activity of Nano-TiN@N–C for Hydrogen Storage in NaAlH₄