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Naji, M. |
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Motta, Antonella |
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Aletan, Dirar |
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Mohamed, Tarek |
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Ertürk, Emre |
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Taccardi, Nicola |
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Kononenko, Denys |
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Petrov, R. H. | Madrid |
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Alshaaer, Mazen | Brussels |
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Bih, L. |
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Casati, R. |
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Muller, Hermance |
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Kočí, Jan | Prague |
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Šuljagić, Marija |
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Kalteremidou, Kalliopi-Artemi | Brussels |
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Azam, Siraj |
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Ospanova, Alyiya |
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Blanpain, Bart |
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Ali, M. A. |
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Popa, V. |
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Rančić, M. |
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Ollier, Nadège |
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Azevedo, Nuno Monteiro |
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Landes, Michael |
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Rignanese, Gian-Marco |
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Halcovitch, Nathan Ross
Lancaster University
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (7/7 displayed)
- 2022Efficient solid-state photoswitching of methoxyazobenzene in a metal–organic framework for thermal energy storagecitations
- 2022A structural investigation of organic battery anode materials by NMR crystallographycitations
- 2021Solid-state nuclear magnetic resonance study of polymorphism in tris(8-hydroxyquinolinate)aluminiumcitations
- 2021Effect of Transition Metal Substitution on the Flexibility and Thermal Properties of MOF-Based Solid-Solid Phase Change Materialscitations
- 2020Long-Term Solar Energy Storage under Ambient Conditions in a MOF-Based Solid–Solid Phase-Change Materialcitations
- 2016Towards Robust Electroactive Biomaterials
- 2014Arylspiroborates derived from 4-tert-Butylcatechol and 3,5-Di-tertbutylcatechol and their antimicrobial activitiescitations
Places of action
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article
Effect of Transition Metal Substitution on the Flexibility and Thermal Properties of MOF-Based Solid-Solid Phase Change Materials
Abstract
A series of azobenzene-loaded metal-organic frameworks were synthesized with the general formula M2(BDC)2(DABCO)(AB)x (M = Zn, Co, Ni, and Cu; BDC = 1,4-benzenedicarboxylate; DABCO = 1,4-diazabicyclo[2.2.2]octane; and AB = azobenzene), herein named M-1ABx. Upon occlusion of AB, each framework undergoes guest-induced breathing, whereby the pores contract around the AB molecules forming a narrow-pore (np) framework. The loading level of the framework is found to be very sensitive to the synthetic protocol and although the stable loading level is close to M-1AB1.0, higher loading levels can be achieved for the Zn, Co, and Ni frameworks prior to vacuum treatment, with a maximum composition for the Zn framework of Zn-1AB1.3. The degree of pore contraction upon loading is modulated by the inherent flexibility of the metal-carboxylate paddlewheel unit in the framework, with the Zn-1AB1.0 showing the biggest contraction of 6.2% and the more rigid Cu-1AB1.0 contracting by only 1.7%. Upon heating, each composite shows a temperature-induced phase transition to an open-pore (op) framework, and the enthalpy and onset temperatures of the phase transition are affected by the framework flexibility. For all composites, UV irradiation causes trans → cis isomerization of the occluded AB molecules. The population of cis-AB at the photostationary state and the thermal stability of the occluded cis-AB molecules are also found to correlate with the flexibility of the framework. Over a full heating-cooling cycle between 0 and 200 °C, the energy stored within the metastable cis-AB molecules is released as heat, with a maximum energy density of 28.9 J g-1 for Zn-1AB1.0. These findings suggest that controlled confinement of photoswitches within flexible frameworks is a potential strategy for the development of solid-solid phase change materials for energy storage.