skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors

Abstract

Postsynthetic modification (PSM) in metal-organic frameworks (MOFs) can introduce multiple functionalities and alter the structural function for the desired application. However, the PSM of the coordination site faces the challenges of structural collapse or incompatibility between the original metal site and the newly formed coordination group. Herein, we developed a novel concept of introducing “primary” and “secondary” nodes, coexisting in a water-stable, Zr-based heterometallic MOF, [Zr6(µ3-OH)8(OH)8][CuI4(L1)4]2 (1-SH-a, H2L1 = 6-mercaptopyridine-3-carboxylic acid). The post-synthetic oxidation at the coordination site was successfully achieved in the “secondary” nodes [CuI4(L1)4]4-, while the robust “primary” nodes [Zr6(µ3-OH)8(OH)8]8+ stabilized the whole framework to form [Zr6(µ3-OH)8(OH)8][(CuI0.44CuII0.56(OH)0.56)4(L2)4]2 (1-SO3H, H2L2 = 6-sulfonicotinic acid). PSM of 1-SH-a to form 1-SO3H dramatically tuned the catalytic properties toward the styrene oxide ring-opening reaction to give a regioselectivity of primary alcohol (A) of ~99% compared with 1-SH-a (~71%).

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [3];  [3]; ORCiD logo [2];  [2];  [4]; ORCiD logo [2]; ORCiD logo [2];  [4]; ORCiD logo [2]
  1. Qingdao University of Science and Technology
  2. BATTELLE (PACIFIC NW LAB)
  3. Tianjin Polytechnic University
  4. University of South Florida
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1646834
Report Number(s):
PNNL-SA-148450
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 32; Journal Issue: 12
Country of Publication:
United States
Language:
English

Citation Formats

Han, Yi, Sinnwell, Michael A., Surbella, Robert G., Xue, Wenjuan, Huang, Hongliang, Zheng, Jian, Peng, Bo, Verma, Gaurav, Yang, Yang, Liu, Lili, Ma, Shengqian, and Thallapally, Praveen K. Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors. United States: N. p., 2020. Web. doi:10.1021/acs.chemmater.0c01267.
Han, Yi, Sinnwell, Michael A., Surbella, Robert G., Xue, Wenjuan, Huang, Hongliang, Zheng, Jian, Peng, Bo, Verma, Gaurav, Yang, Yang, Liu, Lili, Ma, Shengqian, & Thallapally, Praveen K. Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors. United States. https://doi.org/10.1021/acs.chemmater.0c01267
Han, Yi, Sinnwell, Michael A., Surbella, Robert G., Xue, Wenjuan, Huang, Hongliang, Zheng, Jian, Peng, Bo, Verma, Gaurav, Yang, Yang, Liu, Lili, Ma, Shengqian, and Thallapally, Praveen K. 2020. "Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors". United States. https://doi.org/10.1021/acs.chemmater.0c01267.
@article{osti_1646834,
title = {Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal-Organic Framework: Tuning Catalytic Behaviors},
author = {Han, Yi and Sinnwell, Michael A. and Surbella, Robert G. and Xue, Wenjuan and Huang, Hongliang and Zheng, Jian and Peng, Bo and Verma, Gaurav and Yang, Yang and Liu, Lili and Ma, Shengqian and Thallapally, Praveen K.},
abstractNote = {Postsynthetic modification (PSM) in metal-organic frameworks (MOFs) can introduce multiple functionalities and alter the structural function for the desired application. However, the PSM of the coordination site faces the challenges of structural collapse or incompatibility between the original metal site and the newly formed coordination group. Herein, we developed a novel concept of introducing “primary” and “secondary” nodes, coexisting in a water-stable, Zr-based heterometallic MOF, [Zr6(µ3-OH)8(OH)8][CuI4(L1)4]2 (1-SH-a, H2L1 = 6-mercaptopyridine-3-carboxylic acid). The post-synthetic oxidation at the coordination site was successfully achieved in the “secondary” nodes [CuI4(L1)4]4-, while the robust “primary” nodes [Zr6(µ3-OH)8(OH)8]8+ stabilized the whole framework to form [Zr6(µ3-OH)8(OH)8][(CuI0.44CuII0.56(OH)0.56)4(L2)4]2 (1-SO3H, H2L2 = 6-sulfonicotinic acid). PSM of 1-SH-a to form 1-SO3H dramatically tuned the catalytic properties toward the styrene oxide ring-opening reaction to give a regioselectivity of primary alcohol (A) of ~99% compared with 1-SH-a (~71%).},
doi = {10.1021/acs.chemmater.0c01267},
url = {https://www.osti.gov/biblio/1646834}, journal = {Chemistry of Materials},
number = 12,
volume = 32,
place = {United States},
year = {Tue Jun 23 00:00:00 EDT 2020},
month = {Tue Jun 23 00:00:00 EDT 2020}
}