Iodine Adsorption in a Redox-Active Metal-Organic Framework: Electrical Conductivity Induced by Host-Guest Charge-Transfer

Xinran Zhang; Ivan Da Silva; Rodrigo Fazzi; Alena M. Sheveleva; Xue Han; Ben F. Spencer; Sergey A. Sapchenko; Floriana Tuna; Eric J.L. McInnes; Ming Li; Sihai Yang; Martin Schröder

doi:10.1021/acs.inorgchem.9b02176

Iodine Adsorption in a Redox-Active Metal-Organic Framework: Electrical Conductivity Induced by Host-Guest Charge-Transfer

Xinran Zhang, Ivan Da Silva, Rodrigo Fazzi, Alena M. Sheveleva, Xue Han, Ben F. Spencer, Sergey A. Sapchenko, Floriana Tuna, Eric J.L. McInnes, Ming Li, Sihai Yang, Martin Schröder

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

21 Цитирования (Scopus)

Аннотация

We report a comparative study of the binding of I₂ (iodine) in a pair of redox-active metal-organic framework (MOF) materials, MFM-300(V^III) and its oxidized, deprotonated analogue, MFM-300(V^IV). Adsorption of I₂ in MFM-300(V^III) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the V^III centers in the host framework and formation of I₃ ^- species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δ_σ = 700000) of I₂@MFM-300(V^III/IV) in comparison to MFM-300(V^III). In contrast, no host-guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I₂ in MFM-300(V^IV). High-resolution synchrotron X-ray diffraction of I₂@MFM-300(V^III/IV) confirms the first example of self-aggregation of adsorbed iodine species (I₂ and I₃ ^-) into infinite helical chains within a MOF.

Язык оригинала	английский
Страницы (с-по)	14145-14150
Число страниц	6
Журнал	Inorganic Chemistry
Том	58
Номер выпуска	20
DOI	https://doi.org/10.1021/acs.inorgchem.9b02176
Состояние	Опубликовано - 21 окт. 2019

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10.1021/acs.inorgchem.9b02176

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Zhang, X., Da Silva, I., Fazzi, R., Sheveleva, A. M., Han, X., Spencer, B. F., Sapchenko, S. A., Tuna, F., McInnes, E. J. L., Li, M., Yang, S., & Schröder, M. (2019). Iodine Adsorption in a Redox-Active Metal-Organic Framework: Electrical Conductivity Induced by Host-Guest Charge-Transfer. Inorganic Chemistry, 58(20), 14145-14150. https://doi.org/10.1021/acs.inorgchem.9b02176

@article{59a20763f5c74627bfc620a8825121a1,

title = "Iodine Adsorption in a Redox-Active Metal-Organic Framework: Electrical Conductivity Induced by Host-Guest Charge-Transfer",

abstract = "We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal-organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3 - species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host-guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3 -) into infinite helical chains within a MOF.",

keywords = "GAS SORPTION, VOLATILE IODINE, SINGLE-CRYSTAL, CARBON-DIOXIDE, CAPTURE, CHAINS, CONFINEMENT, RELEASE",

author = "Xinran Zhang and {Da Silva}, Ivan and Rodrigo Fazzi and Sheveleva, {Alena M.} and Xue Han and Spencer, {Ben F.} and Sapchenko, {Sergey A.} and Floriana Tuna and McInnes, {Eric J.L.} and Ming Li and Sihai Yang and Martin Schr{\"o}der",

year = "2019",

month = oct,

day = "21",

doi = "10.1021/acs.inorgchem.9b02176",

language = "English",

volume = "58",

pages = "14145--14150",

journal = "Inorganic Chemistry",

issn = "0020-1669",

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Zhang, X, Da Silva, I, Fazzi, R, Sheveleva, AM, Han, X, Spencer, BF, Sapchenko, SA, Tuna, F, McInnes, EJL, Li, M, Yang, S & Schröder, M 2019, 'Iodine Adsorption in a Redox-Active Metal-Organic Framework: Electrical Conductivity Induced by Host-Guest Charge-Transfer', Inorganic Chemistry, том. 58, № 20, стр. 14145-14150. https://doi.org/10.1021/acs.inorgchem.9b02176

Iodine Adsorption in a Redox-Active Metal-Organic Framework : Electrical Conductivity Induced by Host-Guest Charge-Transfer. / Zhang, Xinran; Da Silva, Ivan; Fazzi, Rodrigo и др.

В: Inorganic Chemistry, Том 58, № 20, 21.10.2019, стр. 14145-14150.

Результат исследования: Научные публикации в периодических изданиях › статья › рецензирование

TY - JOUR

T1 - Iodine Adsorption in a Redox-Active Metal-Organic Framework

T2 - Electrical Conductivity Induced by Host-Guest Charge-Transfer

AU - Zhang, Xinran

AU - Da Silva, Ivan

AU - Fazzi, Rodrigo

AU - Sheveleva, Alena M.

AU - Han, Xue

AU - Spencer, Ben F.

AU - Sapchenko, Sergey A.

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Li, Ming

AU - Yang, Sihai

AU - Schröder, Martin

PY - 2019/10/21

Y1 - 2019/10/21

N2 - We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal-organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3 - species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host-guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3 -) into infinite helical chains within a MOF.

AB - We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal-organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3 - species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host-guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3 -) into infinite helical chains within a MOF.

KW - GAS SORPTION

KW - VOLATILE IODINE

KW - SINGLE-CRYSTAL

KW - CARBON-DIOXIDE

KW - CAPTURE

KW - CHAINS

KW - CONFINEMENT

KW - RELEASE

UR - http://www.scopus.com/inward/record.url?scp=85073108615&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.9b02176

DO - 10.1021/acs.inorgchem.9b02176

M3 - Article

C2 - 31566954

AN - SCOPUS:85073108615

VL - 58

SP - 14145

EP - 14150

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 20

ER -