Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Tuning Active Site Flexibility by Defect Engineering of Graphene Ribbon Edge‐hosted Fe−N 3 Sites

Journal Article · · Angewandte Chemie
 [1];  [2]; ORCiD logo [1];  [3]
  1. Catalysis Center for Energy Innovation University of Delaware Newark DE 19716 USA, Department of Chemical and Biomolecular Engineering University of Delaware Newark DE 19716 USA
  2. College of New Energy and Materials China University of Petroleum (Beijing) Beijing 102249 China
  3. Catalysis Center for Energy Innovation University of Delaware Newark DE 19716 USA
+ Show Author Affiliations

Abstract Nitrogen‐doped, carbon‐supported transition metal catalysts are excellent for several reactions. Structural engineering of M−N x sites to boost catalytic activity is rarely studied. Here, we demonstrate that the structural flexibility of Fe−N 3 site is vital for tuning the electronic structure of Fe atoms and regulating the catalytic transfer hydrogenation (CTH) activity. By introducing carbon defects, we construct Fe−N 3 sites with varying Fe−N bond lengths distinguishable by X‐ray absorption spectroscopy. We investigate the CTH activity by density‐functional theory and microkinetic calculations and reveal that the vertical displacement of the Fe atom out of the plane of the support, induced by the Fe−N 3 distortion, raises the Fe orbital and strengthens binding. We propose that the activity is controlled by the relaxation of the reconstructed site, which is further affected by Fe−N bond length, an excellent activity descriptor. We elucidate the origin of the CTH activity and principles for high‐performing Fe−N−C catalysts by defect engineering.

Sponsoring Organization:
USDOE
OSTI ID:
2246963
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 136 Journal Issue: 5; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (32)

Lewis acidic zeolite Beta catalyst for the Meerwein–Ponndorf–Verley reduction of furfural journal January 2016
Controlling the Oxidation State of Fe-Based Catalysts through Nitrogen Doping toward the Hydrodeoxygenation of m-Cresol journal May 2020
Structure-sensitivity and ensemble effects in reactions of strongly adsorbed intermediates: catalytic dehydrogenation and dehydration of formic acid on nickel journal September 1991
Temperature‐Dependent CO2 Electroreduction over Fe‐N‐C and Ni‐N‐C Single‐Atom Catalysts journal November 2021
Unsaturated edge-anchored Ni single atoms on porous microwave exfoliated graphene oxide for electrochemical CO2 journal April 2019
In Situ / Operando Electrocatalyst Characterization by X-ray Absorption Spectroscopy journal September 2020
Preferentially Engineering FeN 4 Edge Sites onto Graphitic Nanosheets for Highly Active and Durable Oxygen Electrocatalysis in Rechargeable Zn–Air Batteries journal November 2020
Efficient single-atom Ni for catalytic transfer hydrogenation of furfural to furfuryl alcohol journal January 2021
Rational Design of Graphene-Supported Single Atom Catalysts for Hydrogen Evolution Reaction journal January 2019
Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol under Mild Conditions over Zr-MOFs: Exploring the Role of Metal Node Coordination and Modification journal February 2020
X-ray-absorption near-edge structure of 3d transition elements in tetrahedral coordination: The effect of bond-length variation journal September 1985
Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement journal January 2020
Edge-hosted Fe-N3 sites on a multiscale porous carbon framework combining high intrinsic activity with efficient mass transport for oxygen reduction journal November 2021
Spatial control of defect creation in graphene at the nanoscale journal January 2012
Acid-Stable and Active M–N–C Catalysts for the Oxygen Reduction Reaction: The Role of Local Structure journal October 2021
Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells journal July 2022
Insights into the activity of single-atom Fe-N-C catalysts for oxygen reduction reaction journal April 2022
Dynamic Control of Sacrificial Bond Transformation in the Fe−N−C Single‐Atom Catalyst for Molecular Oxygen Reduction journal October 2021
Theoretical transition structures for hydride transfer to methyleneiminium ion from methylamine and dihydropyridine. On the nonlinearity of hydride transfers journal April 1987
Mechanism of the Meerwein−Ponndorf−Verley−Oppenauer (MPVO) Redox Equilibrium on Sn− and Zr−Beta Zeolite Catalysts journal October 2006
Understanding the Activity of Single-Atom Catalysis from Frontier Orbitals journal October 2020
Identification of the Electronic and Structural Dynamics of Catalytic Centers in Single-Fe-Atom Material journal December 2020
Carbon Materials for Catalysis book April 2008
Zn-Nx sites on N-doped carbon for aerobic oxidative cleavage and esterification of C(CO)-C bonds journal August 2021
Highly active, ultra-low loading single-atom iron catalysts for catalytic transfer hydrogenation journal October 2023
Bismuth Single Atoms Resulting from Transformation of Metal–Organic Frameworks and Their Use as Electrocatalysts for CO 2 Reduction journal September 2019
A Durable Nickel Single-Atom Catalyst for Hydrogenation Reactions and Cellulose Valorization under Harsh Conditions journal May 2018
Heterogeneous Catalytic Transfer Hydrogenation as an Effective Pathway in Biomass Upgrading journal January 2016
Accelerating Protonation Kinetics for Ammonia Electrosynthesis on Single Iron Sites Embedded in Carbon with Intrinsic Defects journal August 2022
Inducing Electron Dissipation of Pyridinic N Enabled by Single Ni–N4 Sites for the Reduction of Aldehydes/Ketones with Ethanol journal May 2021
General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities journal January 2018
Transition Structures of Hydride Transfer Reactions of Protonated Pyridinium Ion with 1,4-Dihydropyridine and Protonated Nicotinamide with 1,4-Dihydronicotinamide journal April 1995

Similar Records

Related Subjects