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Title: Uncovering Two Principles of Multivariate Hierarchical Metal–Organic Framework Synthesis via Retrosynthetic Design

Abstract

Multivariate (MTV) hierarchical metal-organic frameworks (MOFs), which contain multiple regions arranged in ordered structures, show promise for applications such as gas separation, size-selective catalysis, and controlled drug delivery. However, the complexity of these hierarchical MOFs is limited by a lack of control during framework assembly. Herein, we report the controlled generation of hierarchical MOF-on-MOF structural formation under the guidance of two design principles, surface functionalization and retrosynthetic techniques for stability control. Accordingly, the tunability of spatial distributions, compositions, and crystal sizes has been achieved in these hierarchical systems. The resulting MOF-on-MOF hierarchical structures represent a unique crystalline porous material which contains a controllable distribution of functional groups and metal clusters that are associated together within a framework composite. This general synthetic approach not only expands the scope and tunability of the traditional MTV strategy to multicomponent materials, but also offers a facile route to introduce variants and sequences to sophisticated three-dimensional hierarchical and cooperative systems. As a proof of concept, the photothermal effects of a porphyrinic core-MOF are exploited to trigger the controlled guest release from a shell- MOF with high guest capacity, highlighting the integrated cooperative behaviors in multivariate hierarchical systems.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [3]
  1. Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States
  2. Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States, College of Chemistry, Tianjin Normal University, Tianjin, 300387, China, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University, Tianjin 300071, China
  3. Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States, Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843-3003, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Texas A & M Univ., College Station, TX (United States); Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy and Carbon Management (FECM); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1485532
Alternate Identifier(s):
OSTI ID: 1508811
Grant/Contract Number:  
SC0001015; FE0026472
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Name: ACS Central Science Journal Volume: 4 Journal Issue: 12; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Feng, Liang, Yuan, Shuai, Li, Jia-Luo, Wang, Kun-Yu, Day, Gregory S., Zhang, Peng, Wang, Ying, and Zhou, Hong-Cai. Uncovering Two Principles of Multivariate Hierarchical Metal–Organic Framework Synthesis via Retrosynthetic Design. United States: N. p., 2018. Web. doi:10.1021/acscentsci.8b00722.
Feng, Liang, Yuan, Shuai, Li, Jia-Luo, Wang, Kun-Yu, Day, Gregory S., Zhang, Peng, Wang, Ying, & Zhou, Hong-Cai. Uncovering Two Principles of Multivariate Hierarchical Metal–Organic Framework Synthesis via Retrosynthetic Design. United States. https://doi.org/10.1021/acscentsci.8b00722
Feng, Liang, Yuan, Shuai, Li, Jia-Luo, Wang, Kun-Yu, Day, Gregory S., Zhang, Peng, Wang, Ying, and Zhou, Hong-Cai. Wed . "Uncovering Two Principles of Multivariate Hierarchical Metal–Organic Framework Synthesis via Retrosynthetic Design". United States. https://doi.org/10.1021/acscentsci.8b00722.
@article{osti_1485532,
title = {Uncovering Two Principles of Multivariate Hierarchical Metal–Organic Framework Synthesis via Retrosynthetic Design},
author = {Feng, Liang and Yuan, Shuai and Li, Jia-Luo and Wang, Kun-Yu and Day, Gregory S. and Zhang, Peng and Wang, Ying and Zhou, Hong-Cai},
abstractNote = {Multivariate (MTV) hierarchical metal-organic frameworks (MOFs), which contain multiple regions arranged in ordered structures, show promise for applications such as gas separation, size-selective catalysis, and controlled drug delivery. However, the complexity of these hierarchical MOFs is limited by a lack of control during framework assembly. Herein, we report the controlled generation of hierarchical MOF-on-MOF structural formation under the guidance of two design principles, surface functionalization and retrosynthetic techniques for stability control. Accordingly, the tunability of spatial distributions, compositions, and crystal sizes has been achieved in these hierarchical systems. The resulting MOF-on-MOF hierarchical structures represent a unique crystalline porous material which contains a controllable distribution of functional groups and metal clusters that are associated together within a framework composite. This general synthetic approach not only expands the scope and tunability of the traditional MTV strategy to multicomponent materials, but also offers a facile route to introduce variants and sequences to sophisticated three-dimensional hierarchical and cooperative systems. As a proof of concept, the photothermal effects of a porphyrinic core-MOF are exploited to trigger the controlled guest release from a shell- MOF with high guest capacity, highlighting the integrated cooperative behaviors in multivariate hierarchical systems.},
doi = {10.1021/acscentsci.8b00722},
journal = {ACS Central Science},
number = 12,
volume = 4,
place = {United States},
year = {Wed Dec 12 00:00:00 EST 2018},
month = {Wed Dec 12 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acscentsci.8b00722

Citation Metrics:
Cited by: 68 works
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Figures / Tables:

Scheme 1 Scheme 1: Preparation of Multivariate Hierarchical Metal−Organic Frameworks through Retrosynthetic Design

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