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Title: Insight into Metal–Organic Framework Reactivity: Chemical Water Oxidation Catalyzed by a [Ru(tpy)(dcbpy)(OH 2 )] 2+ ‐Modified UiO‐67

Abstract

Abstract Investigation of chemical water oxidation was conducted on [Ru(tpy)(dcbpy)(OH 2 )] 2+ (tpy=2,2′:6′,2′′‐terpyridine, dcbpy=5,5′‐dicarboxy‐2,2′‐bipyridine)‐doped UiO‐67 metal–organic framework (MOF). The MOF catalyst exhibited a single‐site reaction pathway with kinetic behavior similar to that of a homogeneous Ru complex. The reaction was first order with respect to both the concentration of the Ru catalyst and ceric ammonium nitrate (CAN), with k cat =3(±2)×10 −3   m −1  s −1 in HNO 3 (pH 0.5). The common degradation pathways of ligand dissociation and dimerization were precluded by MOF incorporation, which led to sustained catalysis and greater reusability as opposed to the molecular catalyst in homogeneous solution. Lastly, at the same loading (ca. 97 nmol mg −1 ), samples of different particle sizes generated the same amount of oxygen (ca. 100 nmol), indicative of in‐MOF reactivity. The results suggest that the rate of redox‐hopping charge transport is sufficient to promote chemistry throughout the MOF particulates.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Department of Chemistry Virginia Polytechnic Institute and State University 800 W. Campus Drive Blacksburg Virginia 24061 USA
  2. Department of Physics Purdue University 525 Northwestern Avenue West Lafayette Indiana 47907 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1416245
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
ChemSusChem
Additional Journal Information:
Journal Name: ChemSusChem Journal Volume: 11 Journal Issue: 2; Journal ID: ISSN 1864-5631
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Lin, Shaoyang, Ravari, Alireza K., Zhu, Jie, Usov, Pavel M., Cai, Meng, Ahrenholtz, Spencer R., Pushkar, Yulia, and Morris, Amanda J. Insight into Metal–Organic Framework Reactivity: Chemical Water Oxidation Catalyzed by a [Ru(tpy)(dcbpy)(OH 2 )] 2+ ‐Modified UiO‐67. Germany: N. p., 2018. Web. doi:10.1002/cssc.201701644.
Lin, Shaoyang, Ravari, Alireza K., Zhu, Jie, Usov, Pavel M., Cai, Meng, Ahrenholtz, Spencer R., Pushkar, Yulia, & Morris, Amanda J. Insight into Metal–Organic Framework Reactivity: Chemical Water Oxidation Catalyzed by a [Ru(tpy)(dcbpy)(OH 2 )] 2+ ‐Modified UiO‐67. Germany. https://doi.org/10.1002/cssc.201701644
Lin, Shaoyang, Ravari, Alireza K., Zhu, Jie, Usov, Pavel M., Cai, Meng, Ahrenholtz, Spencer R., Pushkar, Yulia, and Morris, Amanda J. 2018. "Insight into Metal–Organic Framework Reactivity: Chemical Water Oxidation Catalyzed by a [Ru(tpy)(dcbpy)(OH 2 )] 2+ ‐Modified UiO‐67". Germany. https://doi.org/10.1002/cssc.201701644.
@article{osti_1416245,
title = {Insight into Metal–Organic Framework Reactivity: Chemical Water Oxidation Catalyzed by a [Ru(tpy)(dcbpy)(OH 2 )] 2+ ‐Modified UiO‐67},
author = {Lin, Shaoyang and Ravari, Alireza K. and Zhu, Jie and Usov, Pavel M. and Cai, Meng and Ahrenholtz, Spencer R. and Pushkar, Yulia and Morris, Amanda J.},
abstractNote = {Abstract Investigation of chemical water oxidation was conducted on [Ru(tpy)(dcbpy)(OH 2 )] 2+ (tpy=2,2′:6′,2′′‐terpyridine, dcbpy=5,5′‐dicarboxy‐2,2′‐bipyridine)‐doped UiO‐67 metal–organic framework (MOF). The MOF catalyst exhibited a single‐site reaction pathway with kinetic behavior similar to that of a homogeneous Ru complex. The reaction was first order with respect to both the concentration of the Ru catalyst and ceric ammonium nitrate (CAN), with k cat =3(±2)×10 −3   m −1  s −1 in HNO 3 (pH 0.5). The common degradation pathways of ligand dissociation and dimerization were precluded by MOF incorporation, which led to sustained catalysis and greater reusability as opposed to the molecular catalyst in homogeneous solution. Lastly, at the same loading (ca. 97 nmol mg −1 ), samples of different particle sizes generated the same amount of oxygen (ca. 100 nmol), indicative of in‐MOF reactivity. The results suggest that the rate of redox‐hopping charge transport is sufficient to promote chemistry throughout the MOF particulates.},
doi = {10.1002/cssc.201701644},
url = {https://www.osti.gov/biblio/1416245}, journal = {ChemSusChem},
issn = {1864-5631},
number = 2,
volume = 11,
place = {Germany},
year = {Fri Jan 05 00:00:00 EST 2018},
month = {Fri Jan 05 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1002/cssc.201701644

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Cited by: 30 works
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