Enthalpy–Entropy Correlation for Hydrogen Adsorption on MOFs: Variable‐Temperature FTIR Study of Hydrogen Adsorption on MIL‐100(Cr) and MIL‐101(Cr)

Palomino, Gemma Turnes; Cabello, Carlos Palomino; Areán, C. Otero

doi:10.1002/ejic.201001116

Cited by 25 publications

(18 citation statements)

References 74 publications

(57 reference statements)

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“…The adsorption enthalpy is estimated at approximately −10.5 kJ mol −1 , which is slightly larger than the reported values of −9.5 and −6.9 kJ mol −1 for Cr(F x OH 1−x )-MIL-100 and Cr(F)-MIL-101, respectively. 84 The calculated H 2 stretching frequency is also overestimated by ∼40 cm −1 , with respect to the reported experimental values of −111 and −101 cm −1 . The binding enthalpies and stretching frequencies for the early metals have similar values with the M-CPO-27 series, which exhibit enthalpy values between −10 and −15 kJ mol −1 .…”

Section: ■ Resultsmentioning

confidence: 64%

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: 64%

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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“…Besides molecular adsorption in zeolites, 735,736,742 such a trend, already referred to as entropyenthalpy compensation, has been observed in the literature for a range of chemical processes that involve weak interaction forces such as the formation of weakly associated molecular complexes, 743,744 weak hydrogen bonding 745,746 and Langmuirtype adsorption from solution. Besides molecular adsorption in zeolites, 735,736,742 such a trend, already referred to as entropyenthalpy compensation, has been observed in the literature for a range of chemical processes that involve weak interaction forces such as the formation of weakly associated molecular complexes, 743,744 weak hydrogen bonding 745,746 and Langmuirtype adsorption from solution.…”

Section: Vtir: Theorymentioning

confidence: 83%

“…Assuming Langmuir-type adsorption, we obtain the following equation: 17,39,735,736 y(T) = I(T)/I M = K(T)( p/p 0 )/[1 + K(T)( p/p 0 )] (27) where I M stands for the integrated intensity corresponding to full coverage (y = 1) and p 0 is the reference pressure (usually taken as 1 Torr or 1 mbar, whereas in a few cases some authors have chosen 1 bar, vide infra). Simultaneously, the equilibrium pressure (p) performs the same function for the gas phase.…”

Section: Vtir: Theorymentioning

confidence: 99%

Probing zeolites by vibrational spectroscopies

et al. 2015

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This review addresses the most relevant aspects of vibrational spectroscopies (IR, Raman and INS) applied to zeolites and zeotype materials. Surface Brønsted and Lewis acidity and surface basicity are treated in detail. The role of probe molecules and the relevance of tuning both the proton affinity and the steric hindrance of the probe to fully understand and map the complex site population present inside microporous materials are critically discussed. A detailed description of the methods needed to precisely determine the IR absorption coefficients is given, making IR a quantitative technique. The thermodynamic parameters of the adsorption process that can be extracted from a variable-temperature IR study are described. Finally, cutting-edge space- and time-resolved experiments are reviewed. All aspects are discussed by reporting relevant examples. When available, the theoretical literature related to the reviewed experimental results is reported to support the interpretation of the vibrational spectra on an atomic level.

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“…Finally, we note that the entropy change upon H 2 adsorption can also influence the overall adsorption thermodynamics, and the magnitude of this value is dominated by the loss of the hydrogen gas entropy in the form of translational, vibrational, and rotational degrees of freedom. 35,39,40 However, it is believed that DH has a greater effect on the overall thermodynamics of hydrogen adsorption in adsorbents. As a general rule, increasing the strength of the interaction between the H 2 molecule and the storage material-except for a few special cases and conditions, such as when this increase results in decreased deliverable capacities-appears to enhance overall material performance, and a major thrust of current materials development efforts are focused on strategies to optimize this interaction.…”

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confidence: 99%

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Allendorf

Hulvey

Gennett

et al. 2018

Energy Environ. Sci.

217

187

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Nanoporous adsorbents are a diverse category of solid-state materials that hold considerable promise for vehicular hydrogen storage. Although impressive storage capacities have been demonstrated for several materials, particularly at cryogenic temperatures, materials meeting all of the targets established by the U.S. Department of Energy have yet to be identified. In this Perspective, we provide an overview of the major known and proposed strategies for hydrogen adsorbents, with the aim of guiding ongoing research as well as future new storage concepts. The discussion of each strategy includes current relevant literature, strengths and weaknesses, and outstanding challenges that preclude implementation. We consider in particular metal-organic frameworks (MOFs), including surface area/volume tailoring, open metal sites, and the binding of multiple H 2 molecules to a single metal site. Two related classes of porous framework materials, covalent organic frameworks (COFs) and porous aromatic frameworks (PAFs), are also discussed, as are graphene and graphene oxide and doped porous carbons. We additionally introduce criteria for evaluating the merits of a particular materials design strategy. Computation has become an important tool in the discovery of new storage materials, and a brief introduction to the benefits and limitations of computational predictions of H 2 physisorption is therefore presented. Finally, considerations for the synthesis and characterization of hydrogen storage adsorbents are discussed. IntroductionStorage of hydrogen with sufficient gravimetric and volumetric capacity for vehicular use remains a significant obstacle to the widespread adoption of hydrogen fuel cell electric vehicles (FCEVs). Several FCEV models are now commercially available in limited locations around the world, and in these vehicles hydrogen is stored as a gas at room temperature with a fill Table 1 along with the current performance of 700 bar systems. These values pertain to the entire storage system, which includes the mass and volume of hydrogen in addition to the tank and associated balance-ofplant (BOP) components. Notably, it is physically impossible to meet the 2025 and ultimate volumetric capacity target with pressurized gas, as the density of H 2 gas at 700 bar and room temperature is just 40 g L À1 without accounting for the BOP.The search for solid-state H 2 storage materials that can supplant compressed gas systems has been ongoing for at least two decades. The development of a viable storage material Broader contextThe widespread use of hydrogen as a clean, sustainable energy carrier has the potential to provide several significant benefits, including a reduction in oil dependency and emissions, improved energy security and grid resiliency, and substantial economic opportunities across many sectors. Hydrogen-fueled vehicles are already appearing internationally, and one of the critical enabling technologies for increasing their availability is on-board hydrogen storage. Stakeholders in developing a hydrogen in...

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Enthalpy–Entropy Correlation for Hydrogen Adsorption on MOFs: Variable‐Temperature FTIR Study of Hydrogen Adsorption on MIL‐100(Cr) and MIL‐101(Cr)

Cited by 25 publications

References 74 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

Probing zeolites by vibrational spectroscopies

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

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