Li-Filled, B-Substituted Carbon Clathrates

Zeng, Tao; Hoffmann, Roald; Nesper, Reinhard; Ashcroft, N. W.; Strobel, Timothy A.; Proserpio, Davide M.

doi:10.1021/jacs.5b07883

Cited by 47 publications

(51 citation statements)

References 121 publications

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“…In addition, all five carbon clathrates display a semiconducting electronic structure. Li doping of the B-substituted carbon clathrates reduced the band gaps of the carbon clathrate compounds to the range of 0.6 to 2.9 eV [21].…”

Section: Hybrid Carbon-nitrogen Clathratesmentioning

confidence: 98%

“…Several energetically competitive structures, however, exist for each clathrate type. These authors concluded that B substitution stabilizes the cage structure and substantially lowers the energy cost for inserting Li atoms into the clathrate cages to about −2eV/Li at 1 atm pressure [21]. In addition, all five carbon clathrates display a semiconducting electronic structure.…”

Section: Hybrid Carbon-nitrogen Clathratesmentioning

confidence: 99%

“…Zeng et al [21] also investigated theoretically two possible competing routes for synthesizing Li x C y B x : (1) formation of LiBC and (2) the introduction of C vacancies. The authors indicated that LiBC formation is thermodynamically feasible but the process may be kinetically limited due to structural differences between LiBC and Li x C y B x .…”

Section: Hybrid Carbon-nitrogen Clathratesmentioning

confidence: 99%

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Hybrid Carbon-Based Clathrates for Energy Storage

Chan

2018

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Hybrid carbon-silicon, carbon-nitrogen, and carbon-boron clathrates are new classes of Type I carbon-based clathrates that have been identified by first-principles computational methods by substituting atoms on the carbon clathrate framework with Si, N, and/or B atoms. The hybrid framework is further stabilized by embedding appropriate guest atoms within the cavities of the cage structure. Series of hybrid carbon-silicon, carbon-boron, carbon-nitrogen, and carbon-silicon-nitrogen clathrates have been shown to exhibit small positive values for the energy of formation, indicating that they may be metastable compounds and amenable to fabrication. In this overview article, the energy of formation, elastic properties, and electronic properties of selected hybrid carbon-based clathrates are summarized. Theoretical calculations that explore the potential applications of hybrid carbon-based clathrates as energy storage materials, electronic materials, or hard materials are presented. The computational results identify compositions of hybrid carbon-silicon and carbon-nitrogen clathrates that may be considered as candidate materials for use as either electrode materials for Li-ion batteries or as hydrogen storage materials. Prior processing routes for fabricating selected hybrid carbon-based clathrates are highlighted and the difficulties encountered are discussed.

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Section: Hybrid Carbon-nitrogen Clathratesmentioning

confidence: 98%

Section: Hybrid Carbon-nitrogen Clathratesmentioning

confidence: 99%

Section: Hybrid Carbon-nitrogen Clathratesmentioning

confidence: 99%

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Hybrid Carbon-Based Clathrates for Energy Storage

Chan

2018

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“…Using VASP [19], Zeng et al [21] computed the energy of formation and band gaps for five different Li-filled, B-substituted carbon clathrates, including Li8C38B8 (Type I), Li6C28B6 (Type II), Li7C33B7 (Type IV), Li2C10B2 (Type VII), and Li6C28B6 (Type H) at the ground state. A range of strategies has been utilized to determine the energetics of replacing selected carbon atoms on the framework with boron substitution atoms and Li insertion in order to achieve a lower enthalpy and a more stable clathrate compound.…”

Section: Hybrid Carbon-boron Clathratesmentioning

confidence: 99%

“…Several energetically competitive structures, however, exist for each clathrate type. These authors concluded that B substitution stabilizes the cage structure and lowers substantially the energy cost for inserting Li atoms into the clathrate cages to about -2eV/Li at 1 atom pressure [21]. In addition, all five carbon clathrates display a semiconducting electronic structure.…”

Section: Hybrid Carbon-boron Clathratesmentioning

confidence: 99%

Hybrid Carbon-based Clathrates for Energy Storage

Chan¹

2018

Preprint

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Hybrid carbon-silicon, carbon-nitrogen, and carbon-boron clathrates are new classes of Type I carbon-based clathrates that have been identified by first-principles computational methods by substituting atoms on the carbon clathrate framework with Si, N, and/or B atoms. The hybrid framework is further stabilized by embedding appropriate guest atoms within the cavities of the cage structure. Series of hybrid carbon-silicon, carbon-boron, carbon-nitrogen, and carbon-silicon-nitrogen clathrates have been shown to exhibit small positive values of the energy of formation, indicating that they may be metastable compounds and amenable to fabrication. In this overview article, the energy of formation, elastic properties, and electronic properties of selected hybrid carbon-based clathrates are summarized. Theoretical calculations that explore the potential applications of hybrid carbon-based clathrates as energy storage materials, electronic materials, or hard materials are presented. The computational results identify compositions of hybrid carbon-silicon and carbon-nitrogen clathrates that may be considered candidate materials for use as either electrode materials for Li-ion batteries or as hydrogen storage materials. Prior processing routes for fabricating selected hybrid carbon-based clathrates are highlighted and difficulties encountered are discussed.

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Silicon Clathrate‐Supported Catalysts with Low Work Functions for Ammonia Synthesis

Al Maksoud,

Bacha,

Pixius

et al. 2024

Advanced Materials

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Diamond‐type silicon has a work function of ≈4.8 eV, and conventional n‐ or p‐type doping modifies the value only between 4.6 and 5.05 eV. Here, it is shown that the alkali clathrates AxSi46 have substantially lower work functions approaching 2.6 eV, with clear trends between alkali electropositivity and clathrate cage size. The low work function enables alkali clathrates such as K8Si46 to be effective Haber‐Bosch catalyst supports for NH3 synthesis. The catalytic properties of Si, Ge, and Sn‐based clathrates are investigated while supporting Fe and Ru on the surface. The activity largely scales with the work function, and low activation energies below 60 kJ mol−1 are observed due to strong electron donation effects from the support. Ru metal and Sn clathrates seem to be unsuitable for stability issues. Compared to other similar hydride/electride catalysts, the simple structure and composition combined with stability in air/water make a systematic study of these clathrates possible and open the door to other electron‐rich Zintl phases and related intermetallics as low‐work function materials suitable for catalysis. The observed low work function may also have implications for other existing electronic applications.

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Li-Filled, B-Substituted Carbon Clathrates

Cited by 47 publications

References 121 publications

Hybrid Carbon-Based Clathrates for Energy Storage

Hybrid Carbon-Based Clathrates for Energy Storage

Hybrid Carbon-based Clathrates for Energy Storage

Silicon Clathrate‐Supported Catalysts with Low Work Functions for Ammonia Synthesis

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