Finite-Temperature Hydrogen Adsorption and Desorption Thermodynamics Driven by Soft Vibration Modes

Woo, Sung-Jae; Lee, Jun Young; Yoon, Mina; Kim, Yong Hyun

doi:10.1103/physrevlett.111.066102

Cited by 27 publications

(21 citation statements)

References 34 publications

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“…Comparable values were also reported by Woo et al for various metal-substituted porphyrin systems intercalated in planar graphene. 86 In that work, the highest interaction energies were reported for Ti (−33 kJ mol −1 ) and V (−22 kJ mol −1 ), followed by Ca, Mg, and Zn, with values of approximately −10 kJ mol −1 . The adsorption enthalpies for Ga and In follow different trends.…”

Section: ■ Resultsmentioning

confidence: 91%

Ab InitioStudy of the Adsorption of Small Molecules on Metal–Organic Frameworks with Oxo-centered Trimetallic Building Units: The Role of the Undercoordinated Metal Ion

et al. 2015

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The interactions of H2, CO, CO2, and H2O with the undercoordinated metal centers of the trimetallic oxo-centered M3(III)(μ3-O)(X) (COO)6 moiety are studied by means of wave function and density functional theory. This trimetallic oxo-centered cluster is a common building unit in several metal-organic frameworks (MOFs) such as MIL-100, MIL-101, and MIL-127 (also referred to as soc-MOF). A combinatorial computational screening is performed for a large variety of trimetallic oxo-centered units M3(III)O (M = Al(3+), Sc(3+), V(3+), Cr(3+), Fe(3+), Ga(3+), Rh(3+), In(3+), Ir(3+)) interacting with H2O, H2, CO, and CO2. The screening addresses interaction energies, adsorption enthalpies, and vibrational properties. The results show that the Rh and Ir analogues are very promising materials for gas storage and separations.

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Section: ■ Resultsmentioning

confidence: 91%

Ab InitioStudy of the Adsorption of Small Molecules on Metal–Organic Frameworks with Oxo-centered Trimetallic Building Units: The Role of the Undercoordinated Metal Ion

et al. 2015

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“…Our experimental results suggest a volume change of ~10% near T c at ambient pressure; we estimate P Δ V work of ~0.04 meV/unit cell ( P Δ V work = P external × Δ V , where P external is the barometric pressure 1 atm, Δ V is the volume change) 17 . Thus, the prominent difference in Gibbs free energy between the two phases is dominated by the rotational entropy of NPG molecules 30 .…”

Section: Resultsmentioning

confidence: 99%

Understanding colossal barocaloric effects in plastic crystals

et al. 2020

Nat Commun

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Plastic crystal neopentylglycol (NPG) exhibits colossal barocaloric effects (BCEs) with record-high entropy changes, offering exciting prospects for the field of solid-state cooling through the application of moderate pressures. Here, we show that the intermolecular hydrogen bond plays a key role in the orientational order of NPG molecules, while its broken due to thermal perturbation prominently weakens the activation barrier of orientational disorder. The analysis of hydrogen bond strength, rotational entropy free energy and entropy changes provides insightful understanding of BCEs in order-disorder transition. External pressure reduce the hydsrogen bond length and enhance the activation barrier of orientational disorder, which serves as a route of varying intermolecular interaction to tune the order-disorder transition. Our work provides atomic-scale insights on the orientational order-disorder transition of NPG as the prototypical plastic crystal with BCEs, which is helpful to achieve superior caloric materials by molecular designing in the near future.

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“…A finite temperature transition between the two different phases can be cast into the variation of Gibbs free energy ( 23 ); it consists of changes in the internal energy (Δ U ) and vibrational/rotational Helmholtz free energy [Δ F ( T ) = − TS , where S is the entropy of the system] by neglecting the energy change incorporated with the change in volume at a given pressure. Because the Helmholtz free energy is dominated by soft modes ( 24 ), the prominent difference in Gibbs free energy between the two phases is mainly from the isotropic rotation of FA + . The entropy ( S rot ) of a freely rotating FA + cation is as follows

S_{rot} = \frac{3}{2} k_{B} false{1 + ln false(0.4786 k_{B} italicT \sqrt[3]{I_{1} I_{2} I_{3}} false) false}

where k B and T are the Boltzmann constant and temperature, respectively, and the principal moments of inertia ( I i ) of HC(ND 2 ) 2 + (FA + ) cations are 11.644, 60.161, and 71.806 uÅ 2 , where the unified atomic mass unit, u, is 1.6605 × 10 −27 kg.…”

Section: Resultsmentioning

confidence: 99%

Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite

et al. 2016

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Finite-Temperature Hydrogen Adsorption and Desorption Thermodynamics Driven by Soft Vibration Modes

Cited by 27 publications

References 34 publications

Ab InitioStudy of the Adsorption of Small Molecules on Metal–Organic Frameworks with Oxo-centered Trimetallic Building Units: The Role of the Undercoordinated Metal Ion

Ab InitioStudy of the Adsorption of Small Molecules on Metal–Organic Frameworks with Oxo-centered Trimetallic Building Units: The Role of the Undercoordinated Metal Ion

Understanding colossal barocaloric effects in plastic crystals

Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite

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