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Title: Bridging the Homogeneous-Heterogeneous Divide: Modeling Spin for Reactivity in Single Atom Catalysis

Abstract

Single atom catalysts (SACs) are emergent catalytic materials that have the promise of merging the scalability of heterogeneous catalysts with the high activity and atom economy of homogeneous catalysts. Computational, first-principles modeling can provide essential insight into SAC mechanism and active site configuration, where the sub-nm-scale environment can challenge even the highest-resolution experimental spectroscopic techniques. Nevertheless, the very properties that make SACs attractive in catalysis, such as localized d electrons of the isolated transition metal center, make them challenging to study with conventional computational modeling using density functional theory (DFT). For example, Fe/N-doped graphitic SACs have exhibited spin-state dependent reactivity that remains poorly understood. However, spin-state ordering in DFT is very sensitive to the nature of the functional approximation chosen. In this work, we develop accurate benchmarks from correlated wavefunction theory (WFT) for relevant octahedral complexes. We use those benchmarks to evaluate optimal DFT functional choice for predicting spin state ordering in small octahedral complexes as well as models of pyridinic and pyrrolic nitrogen environments expected in larger SACs. Using these guidelines, we determine Fe/N-doped graphene SAC model properties and reactivity as well as their sensitivities to DFT functional choice. Finally, we conclude with broad recommendations for computational modeling ofmore » open-shell transition metal single-atom catalysts.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1507204
Alternate Identifier(s):
OSTI ID: 1612844
Grant/Contract Number:  
SC0018096; CBET-1704266
Resource Type:
Published Article
Journal Name:
Frontiers in Chemistry
Additional Journal Information:
Journal Name: Frontiers in Chemistry Journal Volume: 7; Journal ID: ISSN 2296-2646
Publisher:
Frontiers Research Foundation
Country of Publication:
Switzerland
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; density functional theory; catalysis; single atom catalysis; spin state crossover; transition metal chemistry

Citation Formats

Liu, Fang, Yang, Tzuhsiung, Yang, Jing, Xu, Eve, Bajaj, Akash, and Kulik, Heather J. Bridging the Homogeneous-Heterogeneous Divide: Modeling Spin for Reactivity in Single Atom Catalysis. Switzerland: N. p., 2019. Web. doi:10.3389/fchem.2019.00219.
Liu, Fang, Yang, Tzuhsiung, Yang, Jing, Xu, Eve, Bajaj, Akash, & Kulik, Heather J. Bridging the Homogeneous-Heterogeneous Divide: Modeling Spin for Reactivity in Single Atom Catalysis. Switzerland. doi:10.3389/fchem.2019.00219.
Liu, Fang, Yang, Tzuhsiung, Yang, Jing, Xu, Eve, Bajaj, Akash, and Kulik, Heather J. Tue . "Bridging the Homogeneous-Heterogeneous Divide: Modeling Spin for Reactivity in Single Atom Catalysis". Switzerland. doi:10.3389/fchem.2019.00219.
@article{osti_1507204,
title = {Bridging the Homogeneous-Heterogeneous Divide: Modeling Spin for Reactivity in Single Atom Catalysis},
author = {Liu, Fang and Yang, Tzuhsiung and Yang, Jing and Xu, Eve and Bajaj, Akash and Kulik, Heather J.},
abstractNote = {Single atom catalysts (SACs) are emergent catalytic materials that have the promise of merging the scalability of heterogeneous catalysts with the high activity and atom economy of homogeneous catalysts. Computational, first-principles modeling can provide essential insight into SAC mechanism and active site configuration, where the sub-nm-scale environment can challenge even the highest-resolution experimental spectroscopic techniques. Nevertheless, the very properties that make SACs attractive in catalysis, such as localized d electrons of the isolated transition metal center, make them challenging to study with conventional computational modeling using density functional theory (DFT). For example, Fe/N-doped graphitic SACs have exhibited spin-state dependent reactivity that remains poorly understood. However, spin-state ordering in DFT is very sensitive to the nature of the functional approximation chosen. In this work, we develop accurate benchmarks from correlated wavefunction theory (WFT) for relevant octahedral complexes. We use those benchmarks to evaluate optimal DFT functional choice for predicting spin state ordering in small octahedral complexes as well as models of pyridinic and pyrrolic nitrogen environments expected in larger SACs. Using these guidelines, we determine Fe/N-doped graphene SAC model properties and reactivity as well as their sensitivities to DFT functional choice. Finally, we conclude with broad recommendations for computational modeling of open-shell transition metal single-atom catalysts.},
doi = {10.3389/fchem.2019.00219},
journal = {Frontiers in Chemistry},
number = ,
volume = 7,
place = {Switzerland},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.3389/fchem.2019.00219

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Cited by: 4 works
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  • Angewandte Chemie International Edition, Vol. 54, Issue 47
  • DOI: 10.1002/anie.201507381

Discriminating Catalytically Active FeN x Species of Atomically Dispersed Fe–N–C Catalyst for Selective Oxidation of the C–H Bond
journal, July 2017

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Accurate Spin-State Energetics of Transition Metal Complexes. 1. CCSD(T), CASPT2, and DFT Study of [M(NCH) 6 ] 2+ (M = Fe, Co)
journal, October 2012

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Isolated Ni single atoms in graphene nanosheets for high-performance CO 2 reduction
journal, January 2018

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    Works referencing / citing this record:

    Making machine learning a useful tool in the accelerated discovery of transition metal complexes
    journal, July 2019

    • Kulik, Heather J.
    • WIREs Computational Molecular Science, Vol. 10, Issue 1
    • DOI: 10.1002/wcms.1439