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Title: CO Oxidation on Ir1/TiO2: Resolving Ligand Dynamics and Elementary Reaction Steps

Journal Article · · ACS Catalysis
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [3]; ORCiD logo [3]; ORCiD logo [4];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  3. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
+ Show Author Affiliations

Identifying the rate-controlling steps and the evolution of the ligand environment throughout the catalytic cycle on supported single-atom catalysts is crucial to bridge the gap between heterogeneous and homogeneous catalysis. Here we identified the rate-controlling elementary steps for CO oxidation on TiO2-supported Ir single atoms and isolated the corresponding intermediate Ir complexes. Kinetic measurements, operando spectroscopy, and quantum-chemical calculations indicate that the reaction mechanism has two kinetically relevant steps, CO adsorption/oxidation and O2 dissociation. By varying the reaction conditions, three Ir1 complexes (states) along the reaction cycle were isolated and identified using in situ spectroscopy. Furthermore, we show that all the intermediate Ir1 states share a common CO ligand that does not turn over. Finally, this study provides atomic level details on the active, intermediate complexes and reaction cycle of supported single-metal-atom catalysts, thereby offering future possibilities to control the ligand environment and reactivity.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); US Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515; W911NF-19-1-0308; SC0012704
OSTI ID:
1991524
Alternate ID(s):
OSTI ID: 1993758
Report Number(s):
BNL-224650-2023-JAAM; TRN: US2404065
Journal Information:
ACS Catalysis, Vol. 13, Issue 12; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (49)

Pt Atomic Single-Layer Catalyst Embedded in Defect-Enriched Ceria for Efficient CO Oxidation journal November 2022
Chemisorption of CO and Mechanism of CO Oxidation on Supported Platinum Nanoclusters journal March 2011
Generalized Gradient Approximation Made Simple journal October 1996
The synergy between atomically dispersed Pd and cerium oxide for enhanced catalytic properties journal January 2017
Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra journal September 2016
Hybrid functionals based on a screened Coulomb potential journal May 2003
Synergistic Effects for Enhanced Catalysis in a Dual Single-Atom Catalyst journal January 2021
Strong Metal–Support Interactions between Pt Single Atoms and TiO 2 journal May 2020
Catalysis by Supported Single Metal Atoms journal November 2016
A Review of Preparation Methods for Supported Metal Catalysts book January 2017
On the Nature of Support Effects of Metal Dioxides MO 2 (M = Ti, Zr, Hf, Ce, Th) in Single-Atom Gold Catalysts: Importance of Quantum Primogenic Effect journal July 2016
In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation journal March 2019
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Dynamic Role of Gold d-Orbitals during CO Oxidation under Aerobic Conditions journal March 2022
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
Catalytic CO Oxidation on MgAl 2 O 4 -Supported Iridium Single Atoms: Ligand Configuration and Site Geometry journal May 2021
Reductant composition influences the coordination of atomically dispersed Rh on anatase TiO 2 journal January 2020
Excess electron states in reduced bulk anatase TiO2: Comparison of standard GGA, GGA+U, and hybrid DFT calculations journal October 2008
Emergent Behavior in Oxidation Catalysis over Single-Atom Pd on a Reducible CeO2 Support via Mixed Redox Cycles journal October 2022
Performance of Density Functional Theory for Transition Metal Oxygen Bonds journal October 2019
Single-atom catalysis of CO oxidation using Pt1/FeOx journal July 2011
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives journal October 1999
Atomically Dispersed Rhodium on Self-Assembled Phosphotungstic Acid: Structural Features and Catalytic CO Oxidation Properties journal March 2017
Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina journal September 2014
Unraveling the Intermediate Reaction Complexes and Critical Role of Support-Derived Oxygen Atoms in CO Oxidation on Single-Atom Pt/CeO 2 journal July 2021
Synthesis and Structure of Tetrairidium Clusters on TiO 2 Powder:  Characterization by Infrared and Extended X-ray Absorption Fine Structure Spectroscopies journal February 2002
The Metal Hydride Problem of Computational Chemistry: Origins and Consequences journal March 2019
Bridging homogeneous and heterogeneous catalysis by heterogeneous single-metal-site catalysts journal June 2018
Systematic study of first-row transition-metal diatomic molecules: A self-consistent DFT+U approach journal September 2010
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Kinetics of carbon monoxide oxidation on single-crystal palladium, platinum, and iridium journal September 1988
Single-Atom Catalysts across the Periodic Table journal October 2020
Zeolite- and MgO-Supported Molecular Iridium Complexes: Support and Ligand Effects in Catalysis of Ethene Hydrogenation and H–D Exchange in the Conversion of H 2 + D 2 journal October 2011
Isolating Single and Few Atoms for Enhanced Catalysis journal August 2022
Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl2O4 catalysts journal December 2018
High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts journal July 2017
Infrared spectroscopic investigation of the rhodium gem-dicarbonyl surface species journal July 1983
Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density journal January 2020
Bifunctional hydroformylation on heterogeneous Rh-WOx pair site catalysts journal September 2022
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
MgO-Supported Iridium Metal Pair-Site Catalysts Are More Active and Resistant to CO Poisoning than Analogous Single-Site Catalysts for Ethylene Hydrogenation and Hydrogen–Deuterium Exchange journal September 2019
Band theory and Mott insulators: Hubbard U instead of Stoner I journal July 1991
Infrared spectroscopic study on carbon monoxide-induced structural changes of iridium on an alumina support journal September 1990
Tuning Ligand‐Coordinated Single Metal Atoms on TiO 2 and their Dynamic Response during Hydrogenation Catalysis journal June 2021
Structural evolution of atomically dispersed Pt catalysts dictates reactivity journal April 2019
The Inner Shell Spectroscopy beamline at NSLS-II: a facility for in situ and operando X-ray absorption spectroscopy for materials research journal May 2022
A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource journal May 2013
Ligand-coordinated Ir single-atom catalysts stabilized on oxide supports for ethylene hydrogenation and their evolution under a reductive atmosphere journal January 2021
Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts journal November 2017

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
single-atom catalysis
ligand chemistry
CO oxidation
in situ
operando
infrared spectroscopy
X-ray absorption spectroscopy
36 MATERIALS SCIENCE