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Title: [Ti 8 Zr 2 O 12 (COO) 16 ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks

Abstract

Metal–organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti8Zr2O12(COO)16] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti8Zr2O12(COO)16] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.

Authors:
 [1];  [1];  [2];  [3];  [1]; ORCiD logo [4];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [3];  [3]; ORCiD logo [5]
  1. Department of Chemistry, Texas A&,M University, College Station, Texas 77843-3255, United States
  2. Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Suzhou Nano Science and Technology, Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. China
  3. Berzelii Centre EXSELENT on Porous Materials and Inorganic and Structural Chemistry, Department of Materials and Environmental Chemistry, Stockholm University, Stockholm 106 91, Sweden
  4. School of Physics and Optoelectronics, Xiangtan University, Xiangtan 411105, P. R. China
  5. 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)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1410591
Alternate Identifier(s):
OSTI ID: 1470113; OSTI ID: 1508267
Grant/Contract Number:  
SC0001015; FE0026472; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Name: ACS Central Science Journal Volume: 4 Journal Issue: 1; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Yuan, Shuai, Qin, Jun-Sheng, Xu, Hai-Qun, Su, Jie, Rossi, Daniel, Chen, Yuanping, Zhang, Liangliang, Lollar, Christina, Wang, Qi, Jiang, Hai-Long, Son, Dong Hee, Xu, Hongyi, Huang, Zhehao, Zou, Xiaodong, and Zhou, Hong-Cai. [Ti 8 Zr 2 O 12 (COO) 16 ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks. United States: N. p., 2017. Web. https://doi.org/10.1021/acscentsci.7b00497.
Yuan, Shuai, Qin, Jun-Sheng, Xu, Hai-Qun, Su, Jie, Rossi, Daniel, Chen, Yuanping, Zhang, Liangliang, Lollar, Christina, Wang, Qi, Jiang, Hai-Long, Son, Dong Hee, Xu, Hongyi, Huang, Zhehao, Zou, Xiaodong, & Zhou, Hong-Cai. [Ti 8 Zr 2 O 12 (COO) 16 ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks. United States. https://doi.org/10.1021/acscentsci.7b00497
Yuan, Shuai, Qin, Jun-Sheng, Xu, Hai-Qun, Su, Jie, Rossi, Daniel, Chen, Yuanping, Zhang, Liangliang, Lollar, Christina, Wang, Qi, Jiang, Hai-Long, Son, Dong Hee, Xu, Hongyi, Huang, Zhehao, Zou, Xiaodong, and Zhou, Hong-Cai. Wed . "[Ti 8 Zr 2 O 12 (COO) 16 ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks". United States. https://doi.org/10.1021/acscentsci.7b00497.
@article{osti_1410591,
title = {[Ti 8 Zr 2 O 12 (COO) 16 ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks},
author = {Yuan, Shuai and Qin, Jun-Sheng and Xu, Hai-Qun and Su, Jie and Rossi, Daniel and Chen, Yuanping and Zhang, Liangliang and Lollar, Christina and Wang, Qi and Jiang, Hai-Long and Son, Dong Hee and Xu, Hongyi and Huang, Zhehao and Zou, Xiaodong and Zhou, Hong-Cai},
abstractNote = {Metal–organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti8Zr2O12(COO)16] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti8Zr2O12(COO)16] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.},
doi = {10.1021/acscentsci.7b00497},
journal = {ACS Central Science},
number = 1,
volume = 4,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acscentsci.7b00497

Citation Metrics:
Cited by: 26 works
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Figures / Tables:

Figure 1 Figure 1: Coordination compounds based on [Ti8Zr2O12(RCOO)16] cluster. (a) [Zr6O4(OH)4(COO)12] cluster; (b) the relationship between [Zr6O4(OH)4(COO)12] and [Ti8Zr2O12(COO)16] clusters; (c) [Ti8Zr2O12(COO)16] cluster; (d−h) discrete [Ti8Zr2O12(RCOO)16] clusters formed with different carboxylate ligands; (i) and (j) MOFs based on [Ti8Zr2O12(RCOO)16] clusters and different carboxylate linkers.

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