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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]
+ Show Author Affiliations
  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. doi:10.1021/acscentsci.7b00497.
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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
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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.
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@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}
}
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Journal Article:
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https://doi.org/10.1021/acscentsci.7b00497
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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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Works referenced in this record:

Highly active oxide photocathode for photoelectrochemical water reduction
journal, May 2011

  • Paracchino, Adriana; Laporte, Vincent; Sivula, Kevin
  • Nature Materials, Vol. 10, Issue 6
  • DOI: 10.1038/nmat3017

Metal–organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations
journal, January 2015

  • Chughtai, Adeel H.; Ahmad, Nazir; Younus, Hussein A.
  • Chemical Society Reviews, Vol. 44, Issue 19
  • DOI: 10.1039/C4CS00395K

A p-type Ti( iv )-based metal–organic framework with visible-light photo-response
journal, January 2014

  • Gao, Junkuo; Miao, Jianwei; Li, Pei-Zhou
  • Chem. Commun., Vol. 50, Issue 29
  • DOI: 10.1039/C3CC49440C

A Titanium–Organic Framework as an Exemplar of Combining the Chemistry of Metal– and Covalent–Organic Frameworks
journal, March 2016

  • Nguyen, Ha L.; Gándara, Felipe; Furukawa, Hiroyasu
  • Journal of the American Chemical Society, Vol. 138, Issue 13
  • DOI: 10.1021/jacs.6b01233

Electrochemical Photolysis of Water at a Semiconductor Electrode
journal, July 1972

  • Fujishima, Akira; Honda, Kenichi
  • Nature, Vol. 238, Issue 5358, p. 37-38
  • DOI: 10.1038/238037a0

Crystal Engineering of a Microporous, Catalytically Active fcu Topology MOF Using a Custom-Designed Metalloporphyrin Linker
journal, September 2012

  • Meng, Le; Cheng, Qigan; Kim, Chungsik
  • Angewandte Chemie International Edition, Vol. 51, Issue 40
  • DOI: 10.1002/anie.201205603

Electronic origins of photocatalytic activity in d0 metal organic frameworks
journal, March 2016

  • Nasalevich, Maxim A.; Hendon, Christopher H.; Santaclara, Jara G.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep23676

Zr-based metal–organic frameworks: design, synthesis, structure, and applications
journal, January 2016

  • Bai, Yan; Dou, Yibo; Xie, Lin-Hua
  • Chemical Society Reviews, Vol. 45, Issue 8
  • DOI: 10.1039/C5CS00837A

Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs
journal, July 2016

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04501

Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals
journal, May 2011

  • Schaate, Andreas; Roy, Pascal; Godt, Adelheid
  • Chemistry - A European Journal, Vol. 17, Issue 24
  • DOI: 10.1002/chem.201003211

Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006

  • Lewis, N. S.; Nocera, D. G.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
  • DOI: 10.1073/pnas.0603395103

Semiconductor-based Photocatalytic Hydrogen Generation
journal, November 2010

  • Chen, Xiaobo; Shen, Shaohua; Guo, Liejin
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr1001645

A supermolecular building approach for the design and construction of metal–organic frameworks
journal, January 2014

  • Guillerm, Vincent; Kim, Dongwook; Eubank, Jarrod F.
  • Chem. Soc. Rev., Vol. 43, Issue 16
  • DOI: 10.1039/C4CS00135D

Metal–organic frameworks for artificial photosynthesis and photocatalysis
journal, January 2014

Synthesis and O 2 Reactivity of a Titanium(III) Metal–Organic Framework
journal, October 2015

Metal–Organic Frameworks: Versatile Materials for Heterogeneous Photocatalysis
journal, October 2016

Tunable Rare-Earth fcu-MOFs: A Platform for Systematic Enhancement of CO2 Adsorption Energetics and Uptake
journal, May 2013

  • Xue, Dong-Xu; Cairns, Amy J.; Belmabkhout, Youssef
  • Journal of the American Chemical Society, Vol. 135, Issue 20, p. 7660-7667
  • DOI: 10.1021/ja401429x

An Amine-Functionalized Titanium Metal-Organic Framework Photocatalyst with Visible-Light-Induced Activity for CO2 Reduction
journal, February 2012

  • Fu, Yanghe; Sun, Dengrong; Chen, Yongjuan
  • Angewandte Chemie International Edition, Vol. 51, Issue 14
  • DOI: 10.1002/anie.201108357

Topological Analysis of Metal–Organic Frameworks with Polytopic Linkers and/or Multiple Building Units and the Minimal Transitivity Principle
journal, November 2013

  • Li, Mian; Li, Dan; O’Keeffe, Michael
  • Chemical Reviews, Vol. 114, Issue 2
  • DOI: 10.1021/cr400392k

A New Photoactive Crystalline Highly Porous Titanium(IV) Dicarboxylate
journal, July 2009

  • Dan-Hardi, Meenakshi; Serre, Christian; Frot, Théo
  • Journal of the American Chemical Society, Vol. 131, Issue 31, p. 10857-10859
  • DOI: 10.1021/ja903726m

Water Adsorption in Porous Metal–Organic Frameworks and Related Materials
journal, March 2014

  • Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao
  • Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381
  • DOI: 10.1021/ja500330a

A highly porous metal–organic framework, constructed from a cuboctahedral super-molecular building block, with exceptionally high methane uptake
journal, January 2012

  • Stoeck, Ulrich; Krause, Simon; Bon, Volodymyr
  • Chemical Communications, Vol. 48, Issue 88
  • DOI: 10.1039/c2cc34840c

Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization
journal, July 2013

  • Hendon, Christopher H.; Tiana, Davide; Fontecave, Marc
  • Journal of the American Chemical Society, Vol. 135, Issue 30
  • DOI: 10.1021/ja405350u

A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008

  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
  • DOI: 10.1021/ja8057953

Future Porous Materials
journal, March 2017

Titanium oxo-clusters: precursors for a Lego-like construction of nanostructured hybrid materials
journal, January 2011

  • Rozes, Laurence; Sanchez, Clément
  • Chemical Society Reviews, Vol. 40, Issue 2
  • DOI: 10.1039/c0cs00137f

Solar Water Splitting Cells
journal, November 2010

  • Walter, Michael G.; Warren, Emily L.; McKone, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
  • DOI: 10.1021/cr1002326

Investigating the Case of Titanium(IV) Carboxyphenolate Photoactive Coordination Polymers
journal, June 2016

Studies on Photocatalytic CO 2 Reduction over NH 2 -Uio-66(Zr) and Its Derivatives: Towards a Better Understanding of Photocatalysis on Metal-Organic Frameworks
journal, September 2013

  • Sun, Dengrong; Fu, Yanghe; Liu, Wenjun
  • Chemistry - A European Journal, Vol. 19, Issue 42
  • DOI: 10.1002/chem.201301728

Flexible Zirconium MOF as the Crystalline Sponge for Coordinative Alignment of Dicarboxylates
journal, February 2017

  • Qin, Jun-Sheng; Yuan, Shuai; Alsalme, Ali
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 39
  • DOI: 10.1021/acsami.6b16264

A Titanium–Organic Framework: Engineering of the Band-Gap Energy for Photocatalytic Property Enhancement
journal, December 2016

Titanium coordination compounds: from discrete metal complexes to metal–organic frameworks
journal, January 2017

  • Assi, Hala; Mouchaham, Georges; Steunou, Nathalie
  • Chemical Society Reviews, Vol. 46, Issue 11
  • DOI: 10.1039/C7CS00001D

Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999

  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248

A single crystalline porphyrinic titanium metal–organic framework
journal, January 2015

  • Yuan, Shuai; Liu, Tian-Fu; Feng, Dawei
  • Chemical Science, Vol. 6, Issue 7
  • DOI: 10.1039/C5SC00916B

Visible-Light-Promoted Photocatalytic Hydrogen Production by Using an Amino-Functionalized Ti(IV) Metal–Organic Framework
journal, September 2012

  • Horiuchi, Yu; Toyao, Takashi; Saito, Masakazu
  • The Journal of Physical Chemistry C, Vol. 116, Issue 39
  • DOI: 10.1021/jp3046005

Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
journal, May 2013

  • Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David
  • Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297
  • DOI: 10.1021/ja4050828

Water Stable Zr-Benzenedicarboxylate Metal-Organic Frameworks as Photocatalysts for Hydrogen Generation
journal, August 2010

  • Gomes Silva, Cláudia; Luz, Ignacio; Llabrés i. Xamena, Francesc X.
  • Chemistry - A European Journal, Vol. 16, Issue 36
  • DOI: 10.1002/chem.200903526

Deconstructing the Crystal Structures of Metal–Organic Frameworks and Related Materials into Their Underlying Nets
journal, September 2011

  • O’Keeffe, Michael; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 675-702
  • DOI: 10.1021/cr200205j

A Flexible Photoactive Titanium Metal-Organic Framework Based on a [Ti IV 3 (μ 3 -O)(O) 2 (COO) 6 ] Cluster
journal, September 2015

  • Bueken, Bart; Vermoortele, Frederik; Vanpoucke, Danny E. P.
  • Angewandte Chemie, Vol. 127, Issue 47
  • DOI: 10.1002/ange.201505512
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