Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.chemmater.0c02708
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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Long-Term Solar Energy Storage under Ambient Conditions in a MOF-Based Solid–Solid Phase-Change Material
AU - Griffiths, Kieran
AU - Halcovitch, Nathan
AU - Griffin, John
N1 - This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.chemmater.0c02708
PY - 2020/12/8
Y1 - 2020/12/8
N2 - This paper demonstrates a metal−organic framework (MOF) containing photoswitches within the pores as a hybrid solar thermal fuel (STF) and solid−solid phase-change material (ss-PCM). A series of azobenzene-loaded MOFs were synthesized with the general formula Zn2(BDC)2(DABCO)(AB)x(BDC = 1,4-benzenedicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane, AB = azobenzene, where x = 1.0, 0.9,0.5, 0.3), herein named 1⊃AB1.0, 1⊃AB0.9, 1⊃AB0.5, and 1⊃AB0.3 respectively. X-ray powder diffraction, solid-state NMR, and density functional theory calculations were used to explore in detail the structural changes of the host framework that take place upon loading with the AB guest molecules. Differential scanning calorimetry measurements reveal a reversible phase change, which is absent from the evacuated framework. Upon irradiation with 365 nm light, 40% of the AB guests converted from the trans to the higher-energy cis isomeric form in 1⊃AB1.0. The energy stored within the metastable cis isomers is released upon heating and balances the endotherm associated with the phase transition.However, the exotherm associated with the phase transition is retained upon cooling, resulting in a net energy release over a full heating−cooling cycle. The maximum energy density is observed for the fully loaded composite 1⊃AB1.0, which releases 28.9 J g−1.In addition, the cis-AB guests in this composite showed negligible thermal reconversion during 4 months at ambient temperature, with an estimated energy storage half-life of 4.5 years. Further development of MOF-based STF-ss-PCMs could lead to applications for solar energy conversion and storage, and thermal management.
AB - This paper demonstrates a metal−organic framework (MOF) containing photoswitches within the pores as a hybrid solar thermal fuel (STF) and solid−solid phase-change material (ss-PCM). A series of azobenzene-loaded MOFs were synthesized with the general formula Zn2(BDC)2(DABCO)(AB)x(BDC = 1,4-benzenedicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane, AB = azobenzene, where x = 1.0, 0.9,0.5, 0.3), herein named 1⊃AB1.0, 1⊃AB0.9, 1⊃AB0.5, and 1⊃AB0.3 respectively. X-ray powder diffraction, solid-state NMR, and density functional theory calculations were used to explore in detail the structural changes of the host framework that take place upon loading with the AB guest molecules. Differential scanning calorimetry measurements reveal a reversible phase change, which is absent from the evacuated framework. Upon irradiation with 365 nm light, 40% of the AB guests converted from the trans to the higher-energy cis isomeric form in 1⊃AB1.0. The energy stored within the metastable cis isomers is released upon heating and balances the endotherm associated with the phase transition.However, the exotherm associated with the phase transition is retained upon cooling, resulting in a net energy release over a full heating−cooling cycle. The maximum energy density is observed for the fully loaded composite 1⊃AB1.0, which releases 28.9 J g−1.In addition, the cis-AB guests in this composite showed negligible thermal reconversion during 4 months at ambient temperature, with an estimated energy storage half-life of 4.5 years. Further development of MOF-based STF-ss-PCMs could lead to applications for solar energy conversion and storage, and thermal management.
U2 - 10.1021/acs.chemmater.0c02708
DO - 10.1021/acs.chemmater.0c02708
M3 - Journal article
VL - 32
SP - 9925
EP - 9936
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 23
ER -