Catalytic manganese oxide nanostructures for the reverse water gas shift reaction
Abstract
Understanding the fundamental structure–property relationships of nanomaterials is critical for many catalytic applications as they comprise of the catalyst designing principles. In this paper, we develop efficient synthetic methods to prepare various MnO2 structures and investigate their catalytic performance as applied to the reverse Water Gas Shift (rWGS) reaction. We show that the support-free MnO derived from MnO2 1D, 2D and 3D nanostructures are highly selective (100% CO2 to CO), thermally stable catalysts (850 °C) and differently effective in the rWGS. Up to 50% conversion is observed, with a H2/CO2 feed-in ratio of 1 : 1. From both experiments and DFT calculations, we find the MnO2 morphology plays a critical role in governing the catalytic behaviors since it affects the predominant facets exposed under reaction conditions as well as the intercalation of K+ as a structural building block, substantially affecting the gas-solid interactions. The relative adsorption energy of reactant (CO2) and product (CO), ΔE = Eads(CO2) - Eads(CO), is found to correlate linearly with the catalytic activity, implying a structure–function relationship. Lastly, the strong correlation found between Eads(CO2) - Eads(CO), or more generally, Eads(R) - Eads(P), and catalytic activity makes ΔE a useful descriptor for characterization of efficient catalysts involvingmore »
- Authors:
-
- Yale Univ., New Haven, CT (United States)
- Nankai Univ., Tianjin (China)
- Univ. of Connecticut, Storrs, CT (United States)
- Publication Date:
- Research Org.:
- Univ. of Connecticut, Storrs, CT (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Army Research Laboratory; US Air Force Office of Scientific Research (AFOSR)
- OSTI Identifier:
- 1598231
- Grant/Contract Number:
- FG02-86ER13622; 64935; FA9550-13-1-0020
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanoscale
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 35; Journal ID: ISSN 2040-3364
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
He, Yulian, Yang, Ke R., Yu, Ziwei, Fishman, Zachary S., Achola, Laura A., Tobin, Zachary M., Heinlein, Jake A., Hu, Shu, Suib, Steven L., Batista, Victor S., and Pfefferle, Lisa D. Catalytic manganese oxide nanostructures for the reverse water gas shift reaction. United States: N. p., 2019.
Web. doi:10.1039/c9nr06078b.
He, Yulian, Yang, Ke R., Yu, Ziwei, Fishman, Zachary S., Achola, Laura A., Tobin, Zachary M., Heinlein, Jake A., Hu, Shu, Suib, Steven L., Batista, Victor S., & Pfefferle, Lisa D. Catalytic manganese oxide nanostructures for the reverse water gas shift reaction. United States. https://doi.org/10.1039/c9nr06078b
He, Yulian, Yang, Ke R., Yu, Ziwei, Fishman, Zachary S., Achola, Laura A., Tobin, Zachary M., Heinlein, Jake A., Hu, Shu, Suib, Steven L., Batista, Victor S., and Pfefferle, Lisa D. Tue .
"Catalytic manganese oxide nanostructures for the reverse water gas shift reaction". United States. https://doi.org/10.1039/c9nr06078b. https://www.osti.gov/servlets/purl/1598231.
@article{osti_1598231,
title = {Catalytic manganese oxide nanostructures for the reverse water gas shift reaction},
author = {He, Yulian and Yang, Ke R. and Yu, Ziwei and Fishman, Zachary S. and Achola, Laura A. and Tobin, Zachary M. and Heinlein, Jake A. and Hu, Shu and Suib, Steven L. and Batista, Victor S. and Pfefferle, Lisa D.},
abstractNote = {Understanding the fundamental structure–property relationships of nanomaterials is critical for many catalytic applications as they comprise of the catalyst designing principles. In this paper, we develop efficient synthetic methods to prepare various MnO2 structures and investigate their catalytic performance as applied to the reverse Water Gas Shift (rWGS) reaction. We show that the support-free MnO derived from MnO2 1D, 2D and 3D nanostructures are highly selective (100% CO2 to CO), thermally stable catalysts (850 °C) and differently effective in the rWGS. Up to 50% conversion is observed, with a H2/CO2 feed-in ratio of 1 : 1. From both experiments and DFT calculations, we find the MnO2 morphology plays a critical role in governing the catalytic behaviors since it affects the predominant facets exposed under reaction conditions as well as the intercalation of K+ as a structural building block, substantially affecting the gas-solid interactions. The relative adsorption energy of reactant (CO2) and product (CO), ΔE = Eads(CO2) - Eads(CO), is found to correlate linearly with the catalytic activity, implying a structure–function relationship. Lastly, the strong correlation found between Eads(CO2) - Eads(CO), or more generally, Eads(R) - Eads(P), and catalytic activity makes ΔE a useful descriptor for characterization of efficient catalysts involving gas-solid interactions beyond the rWGS.},
doi = {10.1039/c9nr06078b},
journal = {Nanoscale},
number = 35,
volume = 11,
place = {United States},
year = {2019},
month = {8}
}
Web of Science
Figures / Tables:

Works referenced in this record:
Structure–activity relationship of CuO/MnO2 catalysts in CO oxidation
journal, May 2013
- Qian, Kun; Qian, Zhaoxia; Hua, Qing
- Applied Surface Science, Vol. 273
Two dimensional and layered transition metal oxides
journal, December 2016
- Kalantar-zadeh, Kourosh; Ou, Jian Zhen; Daeneke, Torben
- Applied Materials Today, Vol. 5
Account of Nitroarene Reduction with Size- and Facet-Controlled CuO–MnO 2 Nanocomposites
journal, June 2014
- Pal, Jaya; Mondal, Chanchal; Sasmal, Anup Kumar
- ACS Applied Materials & Interfaces, Vol. 6, Issue 12
MnO 2 -based nanostructures for high-performance supercapacitors
journal, January 2015
- Huang, Ming; Li, Fei; Dong, Fan
- Journal of Materials Chemistry A, Vol. 3, Issue 43
Two-Dimensional MnO 2 as a Better Cathode Material for Lithium Ion Batteries
journal, December 2015
- Deng, Shuo; Wang, Lu; Hou, Tingjun
- The Journal of Physical Chemistry C, Vol. 119, Issue 52
Hydrothermal Synthesis and Pseudocapacitance Properties of MnO 2 Nanostructures
journal, November 2005
- Subramanian, V.; Zhu, Hongwei; Vajtai, Robert
- The Journal of Physical Chemistry B, Vol. 109, Issue 43
MnO 2 -Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media †
journal, February 2010
- Cheng, Fangyi; Su, Yi; Liang, Jing
- Chemistry of Materials, Vol. 22, Issue 3
Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO 2 to CO conversion via the reverse water-gas shift reaction
journal, January 2017
- Fishman, Zachary S.; He, Yulian; Yang, Ke R.
- Nanoscale, Vol. 9, Issue 35
Methanation of CO 2 and reverse water gas shift reactions on Ni/SiO 2 catalysts: the influence of particle size on selectivity and reaction pathway
journal, January 2015
- Wu, H. C.; Chang, Y. C.; Wu, J. H.
- Catalysis Science & Technology, Vol. 5, Issue 8
Methanol synthesis from CO2 and H2 over Pd/ZnO/Al2O3: Catalyst structure dependence of methanol selectivity
journal, March 2016
- Xu, Jinghua; Su, Xiong; Liu, Xiaoyan
- Applied Catalysis A: General, Vol. 514
Role of Support in CO2Reforming of CH4to Syngas over Ni Catalysts
journal, September 1996
- Ruckenstein, Eli; Hang Hu, Yun
- Journal of Catalysis, Vol. 162, Issue 2
Study of reverse water gas shift reaction by TPD, TPR and CO2 hydrogenation over potassium-promoted Cu/SiO2 catalyst
journal, January 2003
- Chen, Ching-Shiun; Cheng, Wu-Hsun; Lin, Shou-Shiun
- Applied Catalysis A: General, Vol. 238, Issue 1
Spectrokinetic Investigation of Reverse Water-Gas-Shift Reaction Intermediates over a Pt/CeO 2 Catalyst
journal, December 2004
- Goguet, Alexandre; Meunier, Frederic C.; Tibiletti, Daniele
- The Journal of Physical Chemistry B, Vol. 108, Issue 52
Highly Dispersed Copper over β-Mo 2 C as an Efficient and Stable Catalyst for the Reverse Water Gas Shift (RWGS) Reaction
journal, December 2016
- Zhang, Xiao; Zhu, Xiaobing; Lin, Lili
- ACS Catalysis, Vol. 7, Issue 1
CO2 hydrogenation on Au/TiC, Cu/TiC, and Ni/TiC catalysts: Production of CO, methanol, and methane
journal, November 2013
- Rodriguez, José A.; Evans, Jaime; Feria, Leticia
- Journal of Catalysis, Vol. 307
The Effect of Coadsorbates in Reverse Water-Gas Shift Reaction on ZnO, in Relation to Reactant-Promoted Reaction Mechanism
journal, April 1993
- Shido, T.; Iwasawa, Y.
- Journal of Catalysis, Vol. 140, Issue 2
Low temperature catalytic reverse water gas shift reaction assisted by an electric field
journal, September 2014
- Oshima, Kazumasa; Shinagawa, Tatsuya; Nogami, Yukako
- Catalysis Today, Vol. 232
Understanding the promoter effect of Cu and Cs over highly effective β-Mo2C catalysts for the reverse water-gas shift reaction
journal, May 2019
- Zhang, Q.; Pastor-Pérez, L.; Jin, W.
- Applied Catalysis B: Environmental, Vol. 244
Development of ZnO/Al2O3 catalyst for reverse-water-gas-shift reaction of CAMERE (carbon dioxide hydrogenation to form methanol via a reverse-water-gas-shift reaction) process
journal, March 2001
- Park, Sang-Woo; Joo, Oh-Shim; Jung, Kwang-Deog
- Applied Catalysis A: General, Vol. 211, Issue 1
Designing of highly selective and high-temperature endurable RWGS heterogeneous catalysts: recent advances and the future directions
journal, September 2017
- Su, Xiong; Yang, Xiaoli; Zhao, Bo
- Journal of Energy Chemistry, Vol. 26, Issue 5
CO 2 conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO 2 conversion to liquid fuels
journal, January 2016
- Daza, Yolanda A.; Kuhn, John N.
- RSC Advances, Vol. 6, Issue 55
Preparation of monodispersed NiO particles in SBA-15, and its enhanced selectivity for reverse water gas shift reaction
journal, September 2013
- Lu, Baowang; Kawamoto, Katsuya
- Journal of Environmental Chemical Engineering, Vol. 1, Issue 3
Volcano plots in hydrogen electrocatalysis – uses and abuses
journal, January 2014
- Quaino, Paola; Juarez, Fernanda; Santos, Elizabeth
- Beilstein Journal of Nanotechnology, Vol. 5
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
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
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
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Effect of the damping function in dispersion corrected density functional theory
journal, March 2011
- Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
- Journal of Computational Chemistry, Vol. 32, Issue 7
X-Ray Determination of Electron-Density Distributions in Oxides, MgO, MnO, CoO, and NiO, and Atomic Scattering Factors of their Constituent Atoms
journal, January 1979
- Sasaki, Satoshi; Fujino, Kiyoshi; TakÉUchi, Yoshio
- Proceedings of the Japan Academy. Ser. B: Physical and Biological Sciences, Vol. 55, Issue 2
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
The Scherrer Formula for X-Ray Particle Size Determination
journal, November 1939
- Patterson, A. L.
- Physical Review, Vol. 56, Issue 10
Amorphous MnO 2 as Cathode Material for Sodium-ion Batteries
journal, June 2017
- Zhou, Yirong; Chen, Tong; Zhang, Junxi
- Chinese Journal of Chemistry, Vol. 35, Issue 8
Low-temperature synthesis of δ-MnO2 with large surface area and its capacitance
journal, August 2010
- Zhu, Gang; Li, Hongjuan; Deng, Lingjuan
- Materials Letters, Vol. 64, Issue 16
Hierarchical urchin-shaped α-MnO2 on graphene-coated carbon microfibers: a binder-free electrode for rechargeable aqueous Na–air battery
journal, July 2016
- Khan, Ziyauddin; Park, Seungyoung; Hwang, Soo Min
- NPG Asia Materials, Vol. 8, Issue 7
The structure and ordering of ε-MnO2
journal, March 2006
- Kim, Chang-Hoon; Akase, Zentaro; Zhang, Lichun
- Journal of Solid State Chemistry, Vol. 179, Issue 3
Controllable synthesis of α- and β - MnO 2 : cationic effect on hydrothermal crystallization
journal, April 2008
- Huang, Xingkang; Lv, Dongping; Yue, Hongjun
- Nanotechnology, Vol. 19, Issue 22
Control of manganese dioxide crystallographic structure in the redox reaction between graphene and permanganate ions and their electrochemical performance
journal, January 2015
- Ji, Chenchen; Ren, Haoqi; Yang, Shengchun
- RSC Advances, Vol. 5, Issue 28
Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni
journal, January 2011
- Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P.
- Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730
Comment on “Hydrothermal Synthesis and Pseudocapacitance Properties of α-MnO 2 Hollow Spheres and Hollow Urchins”
journal, March 2008
- Pitchai, Ragupathy; Park, Dae Hoon; Campet, Guy
- The Journal of Physical Chemistry C, Vol. 112, Issue 16
Raman spectra of birnessite manganese dioxides
journal, April 2003
- Julien, C.
- Solid State Ionics, Vol. 159, Issue 3-4
First-principles DFT+U studies of the atomic, electronic, and magnetic structure of α-MnO2 (cryptomelane)
journal, August 2012
- Cockayne, Eric; Li, Lan
- Chemical Physics Letters, Vol. 544
Understanding the “seesaw effect” of interlayered K+ with different structure in manganese oxides for the enhanced formaldehyde oxidation
journal, May 2018
- Wang, Jinlong; Li, Jun; Zhang, Pengyi
- Applied Catalysis B: Environmental, Vol. 224
The reduction and oxidation behaviour of manganese oxides
journal, January 1999
- Stobbe, E. R.; de Boer, B. A.; Geus, J. W.
- Catalysis Today, Vol. 47, Issue 1-4
CO2 valorisation via Reverse Water-Gas Shift reaction using advanced Cs doped Fe-Cu/Al2O3 catalysts
journal, October 2017
- Pastor-Pérez, L.; Baibars, F.; Le Sache, E.
- Journal of CO2 Utilization, Vol. 21
A DFT study of the acid–base properties of anatase TiO2 and tetragonal ZrO2 by adsorption of CO and CO2 probe molecules
journal, October 2016
- Chen, Hsin-Yi Tiffany; Tosoni, Sergio; Pacchioni, Gianfranco
- Surface Science, Vol. 652
Lewis Acido-Basic Interactions between CO 2 and MgO Surface: DFT and DRIFT Approaches
journal, March 2012
- Cornu, Damien; Guesmi, Hazar; Krafft, Jean-Marc
- The Journal of Physical Chemistry C, Vol. 116, Issue 11
CO 2 and SO 2 sorption on the alkali metals doped CaO(100)surface: A DFT-D study
journal, December 2017
- Wang, Wenju; Fan, Lili; Wang, Guoping
- Applied Surface Science, Vol. 425
CuO Surfaces and CO 2 Activation: A Dispersion-Corrected DFT+ U Study
journal, January 2016
- Mishra, Abhishek Kumar; Roldan, Alberto; de Leeuw, Nora H.
- The Journal of Physical Chemistry C, Vol. 120, Issue 4
Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions
journal, September 2010
- Zhai, Y.; Pierre, D.; Si, R.
- Science, Vol. 329, Issue 5999
Promotion effects of potassium on the activity and selectivity of Pt/zeolite catalysts for reverse water gas shift reaction
journal, November 2017
- Yang, Xiaoli; Su, Xiong; Chen, Xiaodong
- Applied Catalysis B: Environmental, Vol. 216
The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis
journal, May 2004
- Bligaard, T.; Nørskov, J. K.; Dahl, S.
- Journal of Catalysis, Vol. 224, Issue 1
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020
- Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng
- Nature Communications, Vol. 11, Issue 1
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020
- Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna
- Scientific Reports, Vol. 10, Issue 1
Lead palladium titanate: A room temperature nanoscale multiferroic thin film
journal, February 2020
- Mishra, K. K.; Instan, Alvaro A.; Kumari, Shalini
- Scientific Reports, Vol. 10, Issue 1
Discovery of Amorphous Iron Hydrides via Novel Quiescent Reaction in Aqueous Solution
journal, April 2020
- Taguchi, Kohei; Shinozaki, Kazuteru; Okumura, Hideyuki
- Scientific Reports, Vol. 10, Issue 1
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