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Title: Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application

Abstract

In this work, we report a zeolitic imidazolate framework (ZIF-67) with remarkable activity for hydrogen evolution reaction (HER) of 40,500 μmol H2/g MOF, which is, to the best of our knowledge, the highest activity achieved by any MOF system. This result necessitated assessment of its atomic-scale mechanistic function for HER using advanced spectroscopy techniques including time-resolved optical (OTA) and in situ X-ray absorption (XAS) spectroscopy. Through the correlation of OTA results with catalytic performance, we demonstrated that the electron transfer (ET) rather than energy transfer (ENT) pathway between photosensitizer and ZIF-67 is the key factor that controls the efficiency of HER activity, as HER activity that undergoes ET pathway is 3 orders of magnitude higher than that of ENT process. Here, using in situ XAS, we unraveled the spectral features for key intermediate species which are likely responsible for the rate determining process under turn over conditions. Finally, this work represents an original approach to study porous ZIF materials at the molecular level using advanced spectroscopic techniques, providing unprecedented insights into the photoactive nature of ZIF frameworks.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1]
  1. Marquette Univ., Milwaukee, WI (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1416007
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 7; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; H2 evolution reaction; MOF's; catalytic mechanism; synchrotron; ultrafast spectroscopy

Citation Formats

Pattengale, Brian, Yang, Sizhuo, Lee, Sungsik, and Huang, Jier. Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b02467.
Pattengale, Brian, Yang, Sizhuo, Lee, Sungsik, & Huang, Jier. Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application. United States. https://doi.org/10.1021/acscatal.7b02467
Pattengale, Brian, Yang, Sizhuo, Lee, Sungsik, and Huang, Jier. Thu . "Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application". United States. https://doi.org/10.1021/acscatal.7b02467. https://www.osti.gov/servlets/purl/1416007.
@article{osti_1416007,
title = {Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application},
author = {Pattengale, Brian and Yang, Sizhuo and Lee, Sungsik and Huang, Jier},
abstractNote = {In this work, we report a zeolitic imidazolate framework (ZIF-67) with remarkable activity for hydrogen evolution reaction (HER) of 40,500 μmol H2/g MOF, which is, to the best of our knowledge, the highest activity achieved by any MOF system. This result necessitated assessment of its atomic-scale mechanistic function for HER using advanced spectroscopy techniques including time-resolved optical (OTA) and in situ X-ray absorption (XAS) spectroscopy. Through the correlation of OTA results with catalytic performance, we demonstrated that the electron transfer (ET) rather than energy transfer (ENT) pathway between photosensitizer and ZIF-67 is the key factor that controls the efficiency of HER activity, as HER activity that undergoes ET pathway is 3 orders of magnitude higher than that of ENT process. Here, using in situ XAS, we unraveled the spectral features for key intermediate species which are likely responsible for the rate determining process under turn over conditions. Finally, this work represents an original approach to study porous ZIF materials at the molecular level using advanced spectroscopic techniques, providing unprecedented insights into the photoactive nature of ZIF frameworks.},
doi = {10.1021/acscatal.7b02467},
journal = {ACS Catalysis},
number = 12,
volume = 7,
place = {United States},
year = {2017},
month = {11}
}

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Cited by: 21 works
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