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Atomically Dispersed Copper Sites in a Metal–Organic Framework for Reduction of Nitrogen Dioxide

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.1c03036· OSTI ID:1815870
 [1];  [2];  [3];  [2];  [2];  [4];  [5];  [6];  [7];  [7];  [4];  [8];  [8];  [8];  [9];  [4];  [9];  [7];  [6];  [2] more »;  [10] « less
  1. Univ. of Manchester (United Kingdom). Dept. of Chemistry; OSTI
  2. Univ. of Manchester (United Kingdom). Dept. of Chemistry
  3. Univ. of Manchester (United Kingdom). Dept. of Chemistry; Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab. (RAL); Cardiff Univ. (United Kingdom). School of Chemistry
  4. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Neutron Source
  5. Univ. of Manchester (United Kingdom). Dept. of Chemical Engineering and Analytical Science
  6. Univ. of Manchester (United Kingdom). Dept. of Chemical Engineering and Analytical Science
  7. Univ. of Manchester (United Kingdom). Dept. of Materials
  8. Univ. of Manchester (United Kingdom). Dept. of Chemistry; Univ. of Manchester (United Kingdom). Photon Science Inst.
  9. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Sciences Directorate. Neutron Scattering Division
  10. Univ. of Manchester (United Kingdom). Univ. of Manchester (United Kingdom). Dept. of Chemistry
+ Show Author Affiliations

Metal-organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited methods of characterization and lack of direct structural information. Here, we report a comprehensive investigation of the structure and the role of atomically dispersed copper sites in UiO-66 for the catalytic reduction of NO2 at ambient temperature. The atomic dispersion of copper sites on UiO-66 is confirmed by high-angle annular dark-field scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, and inelastic neutron scattering, and their location is identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for the reduction of NO2 at 25 °C without the use of reductants. A selectivity of 88% for the formation of N2 at a 97% conversion of NO2 with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h-1 is achieved under nonthermal plasma activation. In situ and operando infrared, solid-state NMR, and EPR spectroscopy reveal the critical role of copper sites in the adsorption and activation of NO2 molecules, with the formation of {Cu(I)···NO} and {Cu···NO2} adducts promoting the conversion of NO2 to N2. This study will inspire the further design and study of new efficient single-atom catalysts for NO2 abatement via detailed unravelling of their role in catalysis.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1815870
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 29 Vol. 143; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (48)

Definitive Molecular Level Characterization of Defects in UiO-66 Crystals journal August 2015
Extraordinary NO 2 Removal by the Metal-Organic Framework UiO-66-NH 2 journal April 2016
Zirconium-Porphyrin-Based Metal-Organic Framework Hollow Nanotubes for Immobilization of Noble-Metal Single Atoms journal February 2018
Atomically Dispersed Ruthenium Species Inside Metal–Organic Frameworks: Combining the High Activity of Atomic Sites and the Molecular Sieving Effect of MOFs journal March 2019
Regulating the Coordination Environment of MOF‐Templated Single‐Atom Nickel Electrocatalysts for Boosting CO 2 Reduction journal February 2020
Rational Fabrication of Low‐Coordinate Single‐Atom Ni Electrocatalysts by MOFs for Highly Selective CO 2 Reduction journal February 2021
Recent Advances for MOF‐Derived Carbon‐Supported Single‐Atom Catalysts journal February 2019
Selective Catalytic Reduction of NOx with NH3 on Cu-BTC-derived Catalysts: Influence of Modulation and Thermal Treatment journal March 2018
Identification of adsorbed species on Cu-ZSM-5 under NH3 SCR conditions journal May 2007
Synthesis of CuO catalyst derived from HKUST-1 temple for the low-temperature NH3-SCR process journal September 2018
Ultra-efficient removal of NO in a MOFs-NTP synergistic process at ambient temperature journal February 2019
A plasma-assisted catalytic system for NO removal over CuCe/ZSM-5 catalysts at ambient temperature journal April 2017
Hydrothermal stability of CuZSM5 catalyst in reducing NO by NH3 for the urea selective catalytic reduction process journal May 2006
Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3 journal October 2010
Research of copper contained SAPO-34 zeolite for NH 3 -SCR DeNOx by solvent-free synthesis with Cu-TEPA journal November 2016
Catalytic decomposition of NO2 over a copper-decorated metal–organic framework by non-thermal plasma journal February 2021
Atomically Dispersed Metals on Well-Defined Supports including Zeolites and Metal–Organic Frameworks: Structure, Bonding, Reactivity, and Catalysis journal October 2020
Well-Defined Materials for Heterogeneous Catalysis: From Nanoparticles to Isolated Single-Atom Sites journal December 2019
Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives journal March 2020
Metal–Organic Framework-Based Catalysts with Single Metal Sites journal May 2020
Effect of Cosolvent and Temperature on the Structures and Properties of Cu-MOF-74 in Low-temperature NH 3 -SCR journal March 2017
Duet of Acetate and Water at the Defects of Metal–Organic Frameworks journal February 2019
Cerium(IV) Enhances the Catalytic Oxidation Activity of Single-Site Cu Active Sites in MOFs journal June 2020
Spectroscopic Evidence and Density Functional Theory (DFT) Analysis of Low-Temperature Oxidation of Cu + to Cu 2+ NO x in Cu-CHA Catalysts: Implications for the SCR-NO x Reaction Mechanism journal February 2019
Using Transient FTIR Spectroscopy to Probe Active Sites and Reaction Intermediates for Selective Catalytic Reduction of NO on Cu/SSZ-13 Catalysts journal May 2019
NMRShiftDBConstructing a Free Chemical Information System with Open-Source Components journal November 2003
Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory journal April 2011
Structure and Dynamics of the Functionalized MOF Type UiO-66(Zr): NMR and Dielectric Relaxation Spectroscopies Coupled with DFT Calculations journal May 2012
In Situ-DRIFTS Study of Selective Catalytic Reduction of NO x by NH 3 over Cu-Exchanged SAPO-34 journal April 2013
The Determination of the Geometry of Cu(II) Complexes: An EPR Spectroscopy Experiment journal August 2006
Catalytic Dissociation of Nitrogen Dioxide journal April 1965
Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption journal May 2013
Influences of Ligand Environment on the Spectroscopic Properties and Disproportionation Reactivity of Copper−Nitrosyl Complexes journal November 1998
Thermal Cycling of a MOF-Based NO Disproportionation Catalyst journal January 2021
Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal–Organic Framework journal February 2016
Titanium(III)-Oxo Clusters in a Metal–Organic Framework Support Single-Site Co(II)-Hydride Catalysts for Arene Hydrogenation journal December 2017
Synergy of Single-Atom Ni 1 and Ru 1 Sites on CeO 2 for Dry Reforming of CH 4 journal April 2019
Highly Active and Stable Single-Atom Cu Catalysts Supported by a Metal–Organic Framework journal March 2019
Bismuth Single Atoms Resulting from Transformation of Metal–Organic Frameworks and Their Use as Electrocatalysts for CO 2 Reduction journal September 2019
Single-atom catalysis of CO oxidation using Pt1/FeOx journal July 2011
Heterogeneous single-atom catalysis journal May 2018
Copper nanoparticles of well-controlled size and shape: a new advance in synthesis and self-organization journal January 2015
Principles and applications of EPR spectroscopy in the chemical sciences journal January 2018
Cost-effective 17 O enrichment and NMR spectroscopy of mixed-metal terephthalate metal–organic frameworks journal January 2018
Single-atom alloy catalysts: structural analysis, electronic properties and catalytic activities journal January 2021
Reaction of a copper(ii)–nitrosyl complex with hydrogen peroxide: putative formation of a copper(i)–peroxynitrite intermediate journal January 2012
Spin Echoes journal November 1950
www.nmrdb.org: Resurrecting and Processing NMR Spectra On-line journal April 2008

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
Catalysts
Defects
Electron paramagnetic resonance spectroscopy
Nuclear magnetic resonance spectroscopy