Sugar-alcohol@ZIF nanocomposites display suppressed phase-change temperatures

Hackl, Lukas; Hsu, Chih‐Hao; Gordon, Madeleine P.; Chou, Kelly; Ma, Canghai; Kolaczkowski, Matthew A.; Anderson, Christopher L.; Liu, Yi‐Sheng; Guo, Jinghua; Ercius, Peter; Urban, Jeffrey J.

doi:10.1039/d0ta05019a

Cited by 12 publications

(8 citation statements)

References 40 publications

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“…For example, the decrease of the phase transition temperature of poly(ethylene glycol) (PEG) has been observed when incorporated into graphene oxide, nanochannels of porous coordination polymers (PCPs), and carbonized MOFs . Recently, our group experimentally demonstrated the first encapsulation of SAs (erythritol and xylitol) within a class of MOF without an infusion process at room temperature . The nanoconfinement of the sugar alcohols was found to lower the melting point of the SAs into the operating range for water-cooling applications.…”

Section: Introductionmentioning

confidence: 99%

“…18 Recently, our group experimentally demonstrated the first encapsulation of SAs (erythritol and xylitol) within a class of MOF without an infusion process at room temperature. 19 The nanoconfinement of the sugar alcohols was found to lower the melting point of the SAs into the operating range for water cooling applications. However, the mechanism behind the observed melting point depression and the phase identification in the nanopores is currently unknown.…”

Section: Introductionmentioning

confidence: 99%

“…In this study, we investigate the phases of nanoconfined SAs using molecular dynamics (MD) simulations. Despite the observation of thermal transitions of the SA-in-MOF system by differential scanning calorimetry (DSC), 19 the structural difference between the phases consisting of a few number of SA molecules in the nanopores was not explained. Due to the few-nanometer length scales being too small, and lack of experimental access to a MOF pore interior, it is impossible to experimentally observe behaviors of the nanoconfined SAs.…”

Section: ■ Introductionmentioning

confidence: 99%

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Melting Point Depression and Phase Identification of Sugar Alcohols Encapsulated in ZIF Nanopores

2021

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Sugar alcohols (SAs) have attractive characteristics as phase change materials, but their relatively high melting temperature limits their application in the real world. Nanoconfinement can be a useful parameter to reduce the melting temperature to pragmatic ranges. Using molecular dynamics simulations, we investigate the phases and behaviors of encapsulated SA in ZIF-8 and ZIF-11, which cannot be experimentally observed. Based on reliable partial charges for the ZIF structures calculated by a density functional theory, structural analysis shows the SA's attractive interaction to the ZIF structure frustrates the SAs crystallization, and also elucidates the second-order phase transition between amorphous phases. A methodology is suggested to determine the phase transition temperature of confined materials, and used to quantify the melting temperature depression of the ZIF-confined SAs. We also explored the thermal conductivity of the SA-in-ZIF composites. Phonon frequency analysis verifies that the presence of SA molecules enhances the heat transfer by adding heat pathways between the nanoporous structure of ZIFs.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Melting Point Depression and Phase Identification of Sugar Alcohols Encapsulated in ZIF Nanopores

2021

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“…[16][17][18] The unique structure of MOFs enables them to exhibit excellent optical, electrical, magnetic, and photocatalytic properties, making them useful in energy conversion, storage, and transmission applications. [19] Xu et al [20] reported on an unprecedented nanocomposite PCM, which utilizes non-flammable, non-toxic, and high latent heat sugar alcohols encapsulated in an easily synthesized zeolitic imidazole framework (ZIF) crystals. The phase change temperature and latent heat of the composites were 19.8°C and 285 J/g, respectively.…”

Section: Introductionmentioning

confidence: 99%

Synergistic Enhancement of Phase Change Materials through Three-Dimensional Macropore Lamellar Structured MOF/EG Composite for Solar Energy Storage and Beyond

Xiao

Shi

Geng

et al. 2023

Preprint

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Phase change materials (PCMs) have gained significant attention as thermal energy storage materials for reducing dependence on fossil fuels. However, the leakage caused by long-term molecular motion has become a bottleneck for the further advances of energy storage density and application value. Herein, a novel PCM composite with good shape stability, thermal conductivity and photothermal conversion capability was designed. Given the synergistic or hybridization effect between metal-organic frameworks (MOFs) and expanded graphite (EG) components offered the composite unique capabilities, even with the merits of both. The combination of ZIF-67 and EG in a hybrid structure can effectively prevent particle agglomeration, while simultaneously providing a high specific surface area and pore volume for the adsorption of paraffin wax. Compared to pristine unsupported PCMs, the as-obtained PCM composite possesses a 3-fold enhancement in thermal conductivity, 95.56% photothermal conversion efficiency and excellent shape stability. It demonstrates the potential of MOFs-enhanced PCM composites for thermal energy storage and highlight the importance of synergistic or hybridization strategies in the development of advanced materials for sustainable energy applications.

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“…Sugar alcohols possess large latent heat of melting, while experiencing a large degree of supercooling, − which nominates them as good candidates for supercooling TES. For example, erythritol melts at ∼118 °C with a melting enthalpy of ∼340 J/g and mannitol at ∼167 °C with a melting enthalpy of ∼300 J/g. , However, they cannot operate reliably in a practical scale supercooling TES because spontaneous crystallization occurs in the supercooled state.…”

Section: Introductionmentioning

confidence: 99%

Ionic Mixture of Binary Sugar Alcohols and a Polymer: Composition Optimization for Long-Term Thermal Energy Storage

Turunen

Yazdani

2022

ACS Sustainable Chem. Eng.

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A new cold crystallizing material (NaPP) is analyzed for longterm thermal energy storage (TES). NaPP comprises a mixture of erythritol and mannitol as the binary phase change material (PCM) in the scaffold of polyvinyl alcohol (PVA) cross-linked with sodium citrate (SC). The material demonstrates a unique behavior of stable supercooling and vitrification during cooling and cold crystallization during subsequent heating, which enables a reliable long-term storage of the melting enthalpy and a controllable heat release. The use of several components in the material composition, however, impedes optimization of the thermal properties for the storage. As such, differential scanning calorimetry (DSC) was applied to expose the effect of the material components on the thermal properties, and the mixture experimental methodology (MEM) was used to model and optimize these properties. Successful modeling yielded a linear response for the thermal performance, which was significantly affected by the content of SC. Increasing the amount of SC (from 0 to 18 wt %) elevated the ionic strength of the system, which caused reduction in the amount of active PCM (confirmed by X-ray diffraction and DSC) and coarsening of the surface morphology (revealed by optical and scanning electron microscopies). This was also manifested as gradual disappearance of cold crystallization which limits the use of the material to compositions with the glass-transition temperature below −15 °C. MEM identified the optimal composition as 88.9 wt % PCM and 11.1 wt % SC, which showed a melting enthalpy of 194 J/g at 105 °C. Yet, the composition comprising 80 wt % PCM, 10 wt % PVA, and 10 wt % SC showed both high melting enthalpy (176 J/g) and shape stability facilitating larger scale applications. These compositions demonstrated a temperature increase of 10−20 °C during cold crystallization of a 10 g sample, confirming the suitability of the optimization model and the operation of the new material for long-term TES.

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Sugar-alcohol@ZIF nanocomposites display suppressed phase-change temperatures

Abstract: The synthesis and characterization of phase change materials infused into metal–organic framework crystals to demonstrate high latent heats with suppressed phase change temperatures.

Cited by 12 publications

References 40 publications

Melting Point Depression and Phase Identification of Sugar Alcohols Encapsulated in ZIF Nanopores

Melting Point Depression and Phase Identification of Sugar Alcohols Encapsulated in ZIF Nanopores

Synergistic Enhancement of Phase Change Materials through Three-Dimensional Macropore Lamellar Structured MOF/EG Composite for Solar Energy Storage and Beyond

Ionic Mixture of Binary Sugar Alcohols and a Polymer: Composition Optimization for Long-Term Thermal Energy Storage

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