2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid
Abstract
Abstract Efficiently transforming CO 2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non‐toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO 2 (CO 2 RR) on conventional carbon black‐supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp , , and orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO 2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemicalmore »
- Authors:
-
[2];
[1];
[1]
- School of materials Science and Engineering Georgia Institute of Technology 771 Ferst Dr. Atlanta GA 30332–0245 USA
- Materials and Process Simulation Center California Institute of Technology Pasadena CA 91125 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 2322454
- Grant/Contract Number:
- SC0021266
- Resource Type:
- Published Article
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 136 Journal Issue: 12; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Cho, Jinwon, Medina, Arturo, Saih, Ines, Il Choi, Ji, Drexler, Matthew, Goddard, III, William A., Alamgir, Faisal M., and Jang, Seung Soon. 2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid. Germany: N. p., 2024.
Web. doi:10.1002/ange.202320268.
Cho, Jinwon, Medina, Arturo, Saih, Ines, Il Choi, Ji, Drexler, Matthew, Goddard, III, William A., Alamgir, Faisal M., & Jang, Seung Soon. 2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid. Germany. https://doi.org/10.1002/ange.202320268
Cho, Jinwon, Medina, Arturo, Saih, Ines, Il Choi, Ji, Drexler, Matthew, Goddard, III, William A., Alamgir, Faisal M., and Jang, Seung Soon. Mon .
"2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid". Germany. https://doi.org/10.1002/ange.202320268.
@article{osti_2322454,
title = {2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid},
author = {Cho, Jinwon and Medina, Arturo and Saih, Ines and Il Choi, Ji and Drexler, Matthew and Goddard, III, William A. and Alamgir, Faisal M. and Jang, Seung Soon},
abstractNote = {Abstract Efficiently transforming CO 2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non‐toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO 2 (CO 2 RR) on conventional carbon black‐supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp , , and orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO 2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p‐block elements.},
doi = {10.1002/ange.202320268},
journal = {Angewandte Chemie},
number = 12,
volume = 136,
place = {Germany},
year = {Mon Feb 12 00:00:00 EST 2024},
month = {Mon Feb 12 00:00:00 EST 2024}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/ange.202320268
https://doi.org/10.1002/ange.202320268
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:
Density Functional Theory Study of Oxygen Reduction on Graphene and Platinum Surfaces of Pt–Graphene Hybrids
journal, January 2021
- Choi, Ji Il; Kim, Han Seul; Sohn, Young-Jun
- ACS Applied Nano Materials, Vol. 4, Issue 2
Competition between CO 2 Reduction and Hydrogen Evolution on a Gold Electrode under Well-Defined Mass Transport Conditions
journal, February 2020
- Goyal, Akansha; Marcandalli, Giulia; Mints, Vladislav A.
- Journal of the American Chemical Society, Vol. 142, Issue 9
Formic acid as a hydrogen source – recent developments and future trends
journal, January 2012
- Grasemann, Martin; Laurenczy, Gábor
- Energy & Environmental Science, Vol. 5, Issue 8
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Perovskite Oxides for Cathodic Electrocatalysis of Energy‐Related Gases: From O2 to CO2 and N2
journal, April 2021
- Zhang, Haiyan; Xu, Yu; Lu, Min
- Advanced Functional Materials, Vol. 31, Issue 26
Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008
- Hori, Y.; Vayenas, Constantinos G.; White, Ralph E.
- Modern Aspects of Electrochemistry, p. 89-189
Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media
journal, August 1994
- Hori, Yoshio; Wakebe, Hidetoshi; Tsukamoto, Toshio
- Electrochimica Acta, Vol. 39, Issue 11-12, p. 1833-1839
Metal oxides for the electrocatalytic reduction of carbon dioxide: Mechanism of active sites, composites, interface and defect engineering strategies
journal, November 2022
- Shah, Syed Shoaib Ahmad; Sufyan Javed, Muhammad; Najam, Tayyaba
- Coordination Chemistry Reviews, Vol. 471
Carbon‐Rich Nonprecious Metal Single Atom Electrocatalysts for CO 2 Reduction and Hydrogen Evolution
journal, May 2019
- Wang, Tingting; Zhao, Qidong; Fu, Yuanyuan
- Small Methods, Vol. 3, Issue 10
Discovery of a Ni-Ga catalyst for carbon dioxide reduction to methanol
journal, March 2014
- Studt, Felix; Sharafutdinov, Irek; Abild-Pedersen, Frank
- Nature Chemistry, Vol. 6, Issue 4
The Mechanism of CO and CO 2 Hydrogenation to Methanol over Cu-Based Catalysts
journal, March 2015
- Studt, Felix; Behrens, Malte; Kunkes, Edward L.
- ChemCatChem, Vol. 7, Issue 7
Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces
journal, August 2014
- Kuhl, Kendra P.; Hatsukade, Toru; Cave, Etosha R.
- Journal of the American Chemical Society, Vol. 136, Issue 40
Electrochemical reduction of carbon dioxide at a series of platinum single crystal electrodes
journal, August 2000
- Hoshi, Nagahiro; Hori, Yoshio
- Electrochimica Acta, Vol. 45, Issue 25-26, p. 4263-4270
A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals
journal, October 2015
- Wellendorff, Jess; Silbaugh, Trent L.; Garcia-Pintos, Delfina
- Surface Science, Vol. 640
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
Comparative Hazard and Environmental Assessment for Hydrogen and Formic Acid Production, Storage, and Utilization for Renewables
book, November 2022
- Mardini, Nour; Bicer, Yusuf
- Renewable Energy Based Solutions, p. 755-767
Enhancing CO 2 Electroreduction with the Metal–Oxide Interface
journal, April 2017
- Gao, Dunfeng; Zhang, Yi; Zhou, Zhiwen
- Journal of the American Chemical Society, Vol. 139, Issue 16
Remote epitaxy through graphene enables two-dimensional material-based layer transfer
journal, April 2017
- Kim, Yunjo; Cruz, Samuel S.; Lee, Kyusang
- Nature, Vol. 544, Issue 7650
Theoretical Insight into the Trends that Guide the Electrochemical Reduction of Carbon Dioxide to Formic Acid
journal, December 2015
- Yoo, Jong Suk; Christensen, Rune; Vegge, Tejs
- ChemSusChem, Vol. 9, Issue 4
Storage of Renewable Energy by Reduction of CO2 with Hydrogen
journal, May 2015
- Züttel, Andreas; Mauron, Philippe; Kato, Shunsuke
- CHIMIA, Vol. 69, Issue 5
mBEEF-vdW: Robust fitting of error estimation density functionals
journal, June 2016
- Lundgaard, Keld T.; Wellendorff, Jess; Voss, Johannes
- Physical Review B, Vol. 93, Issue 23
Electrochemical CO 2 Reduction Reaction on M@Cu(211) Bimetallic Single-Atom Surface Alloys: Mechanism, Kinetics, and Catalyst Screening
journal, November 2019
- Feng, Yonghao; An, Wei; Wang, Zeming
- ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 1
Competition between CO 2 Reduction and H 2 Evolution on Transition-Metal Electrocatalysts
journal, September 2014
- Zhang, Yin-Jia; Sethuraman, Vijay; Michalsky, Ronald
- ACS Catalysis, Vol. 4, Issue 10
Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites
journal, May 2014
- Karamad, Mohammadreza; Tripkovic, Vladimir; Rossmeisl, Jan
- ACS Catalysis, Vol. 4, Issue 7
Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012
- Wellendorff, Jess; Lundgaard, Keld T.; Møgelhøj, Andreas
- Physical Review B, Vol. 85, Issue 23
Formic Acid as a Hydrogen Energy Carrier
journal, December 2016
- Eppinger, Jörg; Huang, Kuo-Wei
- ACS Energy Letters, Vol. 2, Issue 1
Understanding Selectivity for the Electrochemical Reduction of Carbon Dioxide to Formic Acid and Carbon Monoxide on Metal Electrodes
journal, June 2017
- Feaster, Jeremy T.; Shi, Chuan; Cave, Etosha R.
- ACS Catalysis, Vol. 7, Issue 7
Tuning the electron structure enables the NiZn alloy for CO2 electroreduction to formate
journal, December 2021
- Zhang, Xiaodong; Zhou, Yajiao; Zhang, Hang
- Journal of Energy Chemistry, Vol. 63
Dramatic HER Suppression on Ag Electrodes via Molecular Films for Highly Selective CO 2 to CO Reduction
journal, March 2021
- Thevenon, Arnaud; Rosas-Hernández, Alonso; Fontani Herreros, Alex M.
- ACS Catalysis, Vol. 11, Issue 8
Power to formic acid
book, January 2021
- Chatterjee, Sudipta; Dutta, Indranil; Huang, Kuo-Wei
- Power to Fuel: How to Speed Up a Hydrogen Economy, p. 169-210
Trends of Electrochemical CO 2 Reduction Reaction on Transition Metal Oxide Catalysts
journal, April 2018
- Tayyebi, Ebrahim; Hussain, Javed; Abghoui, Younes
- The Journal of Physical Chemistry C, Vol. 122, Issue 18
Nanosized LaInO3 perovskite for efficient electrocatalytic reduction of CO2 to formate
journal, February 2023
- Zhu, Yuxiao; Zhou, Wei; Dong, Zichao
- Journal of CO2 Utilization, Vol. 68
Inversely Tuning the CO
2
Electroreduction and Hydrogen Evolution Activity on Metal Oxide via Heteroatom Doping
journal, February 2021
- Wang, Jiajun; Wang, Guangjin; Zhang, Jinfeng
- Angewandte Chemie International Edition, Vol. 60, Issue 14
Formic Acid Dehydrogenation Using Noble-Metal Nanoheterogeneous Catalysts: Towards Sustainable Hydrogen-Based Energy
journal, March 2022
- Al-Nayili, Abbas; Majdi, Hasan Sh.; Albayati, Talib M.
- Catalysts, Vol. 12, Issue 3
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
Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO 2 Reduction to CO
journal, January 2013
- Hansen, Heine A.; Varley, Joel B.; Peterson, Andrew A.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 3
Grain-Boundary-Engineered La2CuO4 Perovskite Nanobamboos for Efficient CO2 Reduction Reaction
journal, January 2021
- Wang, Juan; Cheng, Chen; Huang, Bolong
- Nano Letters, Vol. 21, Issue 2
Activation of Transition Metal (Fe, Co and Ni)‐Oxide Nanoclusters by Nitrogen Defects in Carbon Nanotube for Selective CO2 Reduction Reaction
journal, March 2022
- Cheng, Yi; Chen, Jinfan; Yang, Chujie
- ENERGY & ENVIRONMENTAL MATERIALS, Vol. 6, Issue 1
Cu@Pt catalysts prepared by galvanic replacement of polyhedral copper nanoparticles for polymer electrolyte membrane fuel cells
journal, May 2019
- Wu, Meixia; Wu, Xin; Zhang, Lei
- Electrochimica Acta, Vol. 306
Alloy Nanocatalysts for the Electrochemical Oxygen Reduction (ORR) and the Direct Electrochemical Carbon Dioxide Reduction Reaction (CO 2 RR)
journal, December 2018
- Kim, Cheonghee; Dionigi, Fabio; Beermann, Vera
- Advanced Materials, Vol. 31, Issue 31
Contiguous and Atomically Thin Pt Film with Supra‐Bulk Behavior Through Graphene‐Imposed Epitaxy
journal, September 2019
- Choi, Ji Il; Abdelhafiz, Ali; Buntin, Parker
- Advanced Functional Materials, Vol. 29, Issue 46
Photoelectrochemical Conversion of Carbon Dioxide (CO 2 ) into Fuels and Value-Added Products
journal, January 2020
- Kumaravel, Vignesh; Bartlett, John; Pillai, Suresh C.
- ACS Energy Letters, Vol. 5, Issue 2
Monodisperse Au Nanoparticles for Selective Electrocatalytic Reduction of CO 2 to CO
journal, October 2013
- Zhu, Wenlei; Michalsky, Ronald; Metin, Önder
- Journal of the American Chemical Society, Vol. 135, Issue 45
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels
journal, January 2010
- Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix
- Energy & Environmental Science, Vol. 3, Issue 9
Epitaxial and atomically thin graphene–metal hybrid catalyst films: the dual role of graphene as the support and the chemically-transparent protective cap
journal, January 2018
- Abdelhafiz, Ali; Vitale, Adam; Buntin, Parker
- Energy & Environmental Science, Vol. 11, Issue 6
Pd–Ag Alloy Electrocatalysts for CO 2 Reduction: Composition Tuning to Break the Scaling Relationship
journal, August 2019
- Zeng, Jiachang; Zhang, Wenbiao; Yang, Yang
- ACS Applied Materials & Interfaces, Vol. 11, Issue 36
Electrochemical CO2 reduction to formic acid on a Pd-based formic acid oxidation catalyst
journal, April 2015
- Kortlever, Ruud; Balemans, Collin; Kwon, Youngkook
- Catalysis Today, Vol. 244
CO and CO2 Hydrogenation to Methanol Calculated Using the BEEF-vdW Functional
journal, December 2012
- Studt, Felix; Abild-Pedersen, Frank; Varley, Joel B.
- Catalysis Letters, Vol. 143, Issue 1
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004
- Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
- The Journal of Physical Chemistry B, Vol. 108, Issue 46
d–sp orbital hybridization: a strategy for activity improvement of transition metal catalysts
journal, January 2022
- Chen, Hui; Wu, Qiannan; Wang, Yanfei
- Chemical Communications, Vol. 58, Issue 56
A Perovskite Electronic Structure Descriptor for Electrochemical CO 2 Reduction and the Competing H 2 Evolution Reaction
journal, September 2019
- Hwang, Jonathan; Akkiraju, Karthik; Corchado-García, Juan
- The Journal of Physical Chemistry C, Vol. 123, Issue 40
Electrochemical Processing of Carbon Dioxide
journal, May 2008
- Oloman, Colin; Li, Hui
- ChemSusChem, Vol. 1, Issue 5, p. 385-391