This content will become publicly available on Sun Nov 10 00:00:00 EST 2024
Morphology Dependent Reactivity of CsO$$x$$ Nanostructures on Au(111): Binding and Hydrogenation of CO2 to HCOOH
Abstract
Cesium oxide (CsO$$x$$) nanostructures grown on Au(111) behave as active centers for CO2 binding and hydrogenation reactions. The morphology and reactivity of these CsO$$x$$ systems were investigated as a function of alkali coverage using scanning tunnelling microscopy (STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and density functional theory (DFT) calculations. STM results show that initially (0.05 - 0.10 ML) cesium oxide clusters (Cs2O2) grow at the elbow sites of the herringbone of Au(111), subsequently transforming into two-dimensional islands with increasing cesium coverage (> 0.15 ML). XPS measurements reveal the presence of suboxidic (Cs$$y$$O; $$y$$ ≥ 2) species for the island structures. The higher coverages of cesium oxide nanostructures contain a lower O/Cs ratio resulting in a stronger binding of CO2. Moreover, the O atoms in the Cs$$y$$O structure undergo a rearrangement upon the adsorption of CO2 which is a reversible phenomenon. Under CO2 hydrogenation conditions, the small Cs2O2 clusters are hydroxylated, thereby preventing the adsorption of CO2. However, the hydroxylation of the higher coverages of Cs$$y$$O did not prevent CO2 adsorption, and the adsorbed CO2 transformed to HCOO species that eventually yield HCOOH. DFT calculations further confirm that the dissociated H2 attacks the C in the adsorbate to produce formate, which is both thermodynamically and kinetically favored during the CO2 reaction with hydroxylated Cs$$y$$O. These results demonstrate that cesium oxide by itself is an excellent catalyst for CO2 hydrogenation that could produce formate, an important intermediate for the generation of value-added species. The role of the alkali oxide nanostructures as active centers, not merely as promoters, may have broad implications wherein the alkali oxides can be considered in the design of materials tuned for specific applications in heterogeneous catalysis.
- Authors:
-
[1];
[1];
[1];
[5];
[5];
[6];
[6]
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Chemistry Division
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Chemistry Division; Loyola University, Chicago, IL (United States)
- Stony Brook University, NY (United States)
- Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Brookhaven National Laboratory (BNL), Upton, NY (United States). Chemistry Division
- National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, New York 11973, United States
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Chemistry Division; Stony Brook University, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
- OSTI Identifier:
- 2222891
- Report Number(s):
- BNL-225034-2023-JAAM
Journal ID: ISSN 1936-0851
- Grant/Contract Number:
- AC02-05CH11231; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 22; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 03 NATURAL GAS; cesium oxide; gold; hydrogen; CO2 hydrogenation; formic acid
Citation Formats
Mehar, Vikram, Liao, Wenjie, Mahapatra, Mausumi, Shi, Rui, Lim, Hojoon, Barba-Nieto, Irene, Hunt, Adrian, Waluyo, Iradwikanari, Liu, Ping, and Rodriguez, José A. Morphology Dependent Reactivity of CsO$x$ Nanostructures on Au(111): Binding and Hydrogenation of CO2 to HCOOH. United States: N. p., 2023.
Web. doi:10.1021/acsnano.3c08324.
Mehar, Vikram, Liao, Wenjie, Mahapatra, Mausumi, Shi, Rui, Lim, Hojoon, Barba-Nieto, Irene, Hunt, Adrian, Waluyo, Iradwikanari, Liu, Ping, & Rodriguez, José A. Morphology Dependent Reactivity of CsO$x$ Nanostructures on Au(111): Binding and Hydrogenation of CO2 to HCOOH. United States. https://doi.org/10.1021/acsnano.3c08324
Mehar, Vikram, Liao, Wenjie, Mahapatra, Mausumi, Shi, Rui, Lim, Hojoon, Barba-Nieto, Irene, Hunt, Adrian, Waluyo, Iradwikanari, Liu, Ping, and Rodriguez, José A. Fri .
"Morphology Dependent Reactivity of CsO$x$ Nanostructures on Au(111): Binding and Hydrogenation of CO2 to HCOOH". United States. https://doi.org/10.1021/acsnano.3c08324.
@article{osti_2222891,
title = {Morphology Dependent Reactivity of CsO$x$ Nanostructures on Au(111): Binding and Hydrogenation of CO2 to HCOOH},
author = {Mehar, Vikram and Liao, Wenjie and Mahapatra, Mausumi and Shi, Rui and Lim, Hojoon and Barba-Nieto, Irene and Hunt, Adrian and Waluyo, Iradwikanari and Liu, Ping and Rodriguez, José A.},
abstractNote = {Cesium oxide (CsO$x$) nanostructures grown on Au(111) behave as active centers for CO2 binding and hydrogenation reactions. The morphology and reactivity of these CsO$x$ systems were investigated as a function of alkali coverage using scanning tunnelling microscopy (STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and density functional theory (DFT) calculations. STM results show that initially (0.05 - 0.10 ML) cesium oxide clusters (Cs2O2) grow at the elbow sites of the herringbone of Au(111), subsequently transforming into two-dimensional islands with increasing cesium coverage (> 0.15 ML). XPS measurements reveal the presence of suboxidic (Cs$y$O; $y$ ≥ 2) species for the island structures. The higher coverages of cesium oxide nanostructures contain a lower O/Cs ratio resulting in a stronger binding of CO2. Moreover, the O atoms in the Cs$y$O structure undergo a rearrangement upon the adsorption of CO2 which is a reversible phenomenon. Under CO2 hydrogenation conditions, the small Cs2O2 clusters are hydroxylated, thereby preventing the adsorption of CO2. However, the hydroxylation of the higher coverages of Cs$y$O did not prevent CO2 adsorption, and the adsorbed CO2 transformed to HCOO species that eventually yield HCOOH. DFT calculations further confirm that the dissociated H2 attacks the C in the adsorbate to produce formate, which is both thermodynamically and kinetically favored during the CO2 reaction with hydroxylated Cs$y$O. These results demonstrate that cesium oxide by itself is an excellent catalyst for CO2 hydrogenation that could produce formate, an important intermediate for the generation of value-added species. The role of the alkali oxide nanostructures as active centers, not merely as promoters, may have broad implications wherein the alkali oxides can be considered in the design of materials tuned for specific applications in heterogeneous catalysis.},
doi = {10.1021/acsnano.3c08324},
journal = {ACS Nano},
number = 22,
volume = 17,
place = {United States},
year = {Fri Nov 10 00:00:00 EST 2023},
month = {Fri Nov 10 00:00:00 EST 2023}
}
Free Publicly Available Full Text
This content will become publicly available on November 10, 2024
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Ultrathin metal films and particles on oxide surfaces: structural, electronic and chemisorptive properties
journal, January 1997
- Campbell, Charles T.
- Surface Science Reports, Vol. 27, Issue 1-3
A Common Single-Site Pt(II)–O(OH) x – Species Stabilized by Sodium on “Active” and “Inert” Supports Catalyzes the Water-Gas Shift Reaction
journal, March 2015
- Yang, Ming; Liu, Jilei; Lee, Sungsik
- Journal of the American Chemical Society, Vol. 137, Issue 10
Alkali-metal-affected adsorption of molecules on metal surfaces
journal, January 1988
- Bonzel, H. P.
- Surface Science Reports, Vol. 8, Issue 2
Promotion of the water gas shift reaction by cesium surface doping of the model binary copper/zinc oxide catalyst
journal, February 1986
- Klier, K.; Young, Chyi Woei; Nunan, John G.
- Industrial & Engineering Chemistry Fundamentals, Vol. 25, Issue 1
Structure of the Cs-induced (1×3) reconstruction of Au(110)
journal, March 1989
- Häberle, Patricio; Fenter, Paul; Gustafsson, Torgny
- Physical Review B, Vol. 39, Issue 9
Activation and Reactions of CO 2 on a K-Promoted Au(111) Surface
journal, October 2009
- Farkas, Arnold Péter; Solymosi, Frigyes
- The Journal of Physical Chemistry C, Vol. 113, Issue 46
Cesium-Induced Active Sites for C–C Coupling and Ethanol Synthesis from CO 2 Hydrogenation on Cu/ZnO(0001̅) Surfaces
journal, July 2021
- Wang, Xuelong; Ramírez, Pedro J.; Liao, Wenjie
- Journal of the American Chemical Society, Vol. 143, Issue 33
Methanol and C2 oxygenate synthesis over cesium doped Cu/ZnO and Cu/ZnO/Al2O3 catalysts: A study of selectivity and 13C incorporation patterns
journal, October 1988
- Nunan, J.
- Journal of Catalysis, Vol. 113, Issue 2
Promotional Effects of Cesium Promoter on Higher Alcohol Synthesis from Syngas over Cesium-Promoted Cu/ZnO/Al 2 O 3 Catalysts
journal, August 2016
- Sun, Jie; Cai, Qiuxia; Wan, Yan
- ACS Catalysis, Vol. 6, Issue 9
Selective C 2+ Alcohol Synthesis from Direct CO 2 Hydrogenation over a Cs-Promoted Cu-Fe-Zn Catalyst
journal, April 2020
- Xu, Di; Ding, Mingyue; Hong, Xinlin
- ACS Catalysis, Vol. 10, Issue 9
Structure and Chemical State of Cesium on Well-Defined Cu(111) and Cu 2 O/Cu(111) Surfaces
journal, January 2020
- Hamlyn, Rebecca C. E.; Mahapatra, Mausumi; Orozco, Ivan
- The Journal of Physical Chemistry C, Vol. 124, Issue 5
The Interaction of K and O2 on Au(111): Multiple Growth Modes of Potassium Oxide and Their Catalytic Activity for CO Oxidation
journal, August 2022
- Shi, Rui; Liao, Wenjie; Ramírez, Pedro J.
- Angewandte Chemie International Edition, Vol. 61, Issue 39
The system K/Au(111): adsorption and surface restructuring
journal, March 1996
- Barth, J. V.; Schuster, R.; Behm, R. J.
- Surface Science, Vol. 348, Issue 3
Ionic oxygen species formed in the presence of lithium, potassium and cesium
journal, January 1992
- Jupille, J.; Dolle, P.; Besançon, M.
- Surface Science, Vol. 260, Issue 1-3
Core-level binding-energy shifts at surfaces and in solids
journal, May 1987
- Egelhoff, W. F.
- Surface Science Reports, Vol. 6, Issue 6-8
Morphology and chemical behavior of model CsO x /Cu 2 O/Cu(111) nanocatalysts for methanol synthesis: Reaction with CO 2 and H 2
journal, January 2020
- Hamlyn, Rebecca; Mahapatra, Mausumi; Orozco, Ivan
- The Journal of Chemical Physics, Vol. 152, Issue 4
Water–Gas Shift Reaction on K/Cu(111) and Cu/K/TiO 2 (110) Surfaces: Alkali Promotion of Water Dissociation and Production of H 2
journal, October 2019
- Rodriguez, José A.; Remesal, Elena R.; Ramírez, Pedro J.
- ACS Catalysis, Vol. 9, Issue 12
Model studies of cesium promoters in water-gas shift catalysts: Cs/Cu(110)
journal, July 1992
- Campbell, J.
- Journal of Catalysis, Vol. 136, Issue 1
Understanding Methanol Synthesis on Inverse ZnO/CuO x /Cu Catalysts: Stability of CH 3 O Species and Dynamic Nature of the Surface
journal, March 2021
- Orozco, Ivan; Huang, Erwei; Mahapatra, Mausumi
- The Journal of Physical Chemistry C, Vol. 125, Issue 12
Theoretical Analysis of Transition-Metal Catalysts for Formic Acid Decomposition
journal, March 2014
- Yoo, Jong Suk; Abild-Pedersen, Frank; Nørskov, Jens K.
- ACS Catalysis, Vol. 4, Issue 4
A fast and robust algorithm for Bader decomposition of charge density
journal, June 2006
- Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes
- Computational Materials Science, Vol. 36, Issue 3
Accurate and efficient algorithm for Bader charge integration
journal, February 2011
- Yu, Min; Trinkle, Dallas R.
- The Journal of Chemical Physics, Vol. 134, Issue 6
Formate adsorption and azimuthal orientation on Cu(100) from molecular orbital theory
journal, September 1989
- Mehandru, S. P.; Anderson, Alfred B.
- Surface Science, Vol. 219, Issue 1-2
Adsorption of the formate species on copper surfaces: a DFT study
journal, July 1999
- Gomes, J. R. B.; Gomes, J. A. N. F.
- Surface Science, Vol. 432, Issue 3
Interfaces in heterogeneous catalytic reactions: Ambient pressure XPS as a tool to unravel surface chemistry
journal, November 2017
- Palomino, Robert M.; Hamlyn, Rebecca; Liu, Zongyuan
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 221
Ambient Pressure X-Ray Photoelectron Spectroscopy at the IOS (23-ID-2) Beamline at the National Synchrotron Light Source II
journal, May 2022
- Waluyo, Iradwikanari; Hunt, Adrian
- Synchrotron Radiation News, Vol. 35, Issue 3
New In-Situ and Operando Facilities for Catalysis Science at NSLS-II: The Deployment of Real-Time, Chemical, and Structure-Sensitive X-ray Probes
journal, March 2017
- Palomino, Robert M.; Stavitski, Eli; Waluyo, Iradwikanari
- Synchrotron Radiation News, Vol. 30, Issue 2
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979