Single‐Site, Single‐Metal‐Atom, Heterogeneous Electrocatalyst: Metal–Organic‐Framework Supported Molybdenum Sulfide for Redox Mediator‐Assisted Hydrogen Evolution Reaction
Abstract
Abstract Synthesis of single‐site catalysts, whereby the local structure and surrounding chemical environments are identical, has been challenging, particularly in heterogeneous catalysis, as the support often presents spectrum of chemically distinct binding sites. Yet, the above criteria are crucial in attributing the apparent catalytic performance to the structural motif. The presented work augments on our previous work using monometallic molybdenum sulfide tethered within a zirconium‐based metal‐organic framework (MOF), NU‐1000; the monometallic nature enables all presented sites to be catalytically addressable. As the molybdenum sulfide species resided within two distinct pores (micro‐ and mesopores) of the MOF support, we have imparted uniformity in the local chemical environment by reducing the pore heterogeneity down to a single mesopore. Single‐site and single‐atom nature of the candidate catalyst was established via X‐ray diffraction measurements. Redox mediators were implemented, which, under reductive potentials, provide reduced species; they can effectively deliver the necessary reducing equivalences to the catalytic units that can otherwise not be addressed electrochemically due to the low electron mobility within the framework. Our results indicate the micropore‐allocated molybdenum sulfide is approximately four times more active as that in mesopores, whereas its catalytic mechanism is identical, underscoring the importance of controlling chemical environment beyondmore »
- Authors:
-
- Department of Chemistry Northwestern University 2145 Sheridan Rd. Evanston IL 60208 USA
- Department of Chemistry Northwestern University 2145 Sheridan Rd. Evanston IL 60208 USA, College of Mechanics and Materials Hohai University Nanjing 210098 China
- Department of Chemical and Biological Engineering Northwestern University 2145 Sheridan Rd. Evanston IL 60208 USA
- Department of Chemistry Northwestern University 2145 Sheridan Rd. Evanston IL 60208 USA, Department of Chemical and Biological Engineering Northwestern University 2145 Sheridan Rd. Evanston IL 60208 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1598745
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- ChemElectroChem
- Additional Journal Information:
- Journal Name: ChemElectroChem Journal Volume: 7 Journal Issue: 2; Journal ID: ISSN 2196-0216
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Noh, Hyunho, Yang, Ying, Zhang, Xuan, Goetjen, Timothy A., Syed, Zoha H., Lu, Zhiyong, Ahn, Sol, Farha, Omar K., and Hupp, Joseph T. Single‐Site, Single‐Metal‐Atom, Heterogeneous Electrocatalyst: Metal–Organic‐Framework Supported Molybdenum Sulfide for Redox Mediator‐Assisted Hydrogen Evolution Reaction. Germany: N. p., 2020.
Web. doi:10.1002/celc.201901650.
Noh, Hyunho, Yang, Ying, Zhang, Xuan, Goetjen, Timothy A., Syed, Zoha H., Lu, Zhiyong, Ahn, Sol, Farha, Omar K., & Hupp, Joseph T. Single‐Site, Single‐Metal‐Atom, Heterogeneous Electrocatalyst: Metal–Organic‐Framework Supported Molybdenum Sulfide for Redox Mediator‐Assisted Hydrogen Evolution Reaction. Germany. https://doi.org/10.1002/celc.201901650
Noh, Hyunho, Yang, Ying, Zhang, Xuan, Goetjen, Timothy A., Syed, Zoha H., Lu, Zhiyong, Ahn, Sol, Farha, Omar K., and Hupp, Joseph T. Mon .
"Single‐Site, Single‐Metal‐Atom, Heterogeneous Electrocatalyst: Metal–Organic‐Framework Supported Molybdenum Sulfide for Redox Mediator‐Assisted Hydrogen Evolution Reaction". Germany. https://doi.org/10.1002/celc.201901650.
@article{osti_1598745,
title = {Single‐Site, Single‐Metal‐Atom, Heterogeneous Electrocatalyst: Metal–Organic‐Framework Supported Molybdenum Sulfide for Redox Mediator‐Assisted Hydrogen Evolution Reaction},
author = {Noh, Hyunho and Yang, Ying and Zhang, Xuan and Goetjen, Timothy A. and Syed, Zoha H. and Lu, Zhiyong and Ahn, Sol and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Abstract Synthesis of single‐site catalysts, whereby the local structure and surrounding chemical environments are identical, has been challenging, particularly in heterogeneous catalysis, as the support often presents spectrum of chemically distinct binding sites. Yet, the above criteria are crucial in attributing the apparent catalytic performance to the structural motif. The presented work augments on our previous work using monometallic molybdenum sulfide tethered within a zirconium‐based metal‐organic framework (MOF), NU‐1000; the monometallic nature enables all presented sites to be catalytically addressable. As the molybdenum sulfide species resided within two distinct pores (micro‐ and mesopores) of the MOF support, we have imparted uniformity in the local chemical environment by reducing the pore heterogeneity down to a single mesopore. Single‐site and single‐atom nature of the candidate catalyst was established via X‐ray diffraction measurements. Redox mediators were implemented, which, under reductive potentials, provide reduced species; they can effectively deliver the necessary reducing equivalences to the catalytic units that can otherwise not be addressed electrochemically due to the low electron mobility within the framework. Our results indicate the micropore‐allocated molybdenum sulfide is approximately four times more active as that in mesopores, whereas its catalytic mechanism is identical, underscoring the importance of controlling chemical environment beyond the active site.},
doi = {10.1002/celc.201901650},
journal = {ChemElectroChem},
number = 2,
volume = 7,
place = {Germany},
year = {Mon Feb 10 00:00:00 EST 2020},
month = {Mon Feb 10 00:00:00 EST 2020}
}
https://doi.org/10.1002/celc.201901650
Web of Science
Works referenced in this record:
The Fischer–Tropsch process: 1950–2000
journal, January 2002
- Dry, Mark E.
- Catalysis Today, Vol. 71, Issue 3-4
Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications
journal, February 2017
- Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong
- Accounts of Chemical Research, Vol. 50, Issue 4
Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide
journal, March 2016
- Tran, Phong D.; Tran, Thu V.; Orio, Maylis
- Nature Materials, Vol. 15, Issue 6
Octahedral vs. trigonal-prismatic coordination and clustering in transition-metal dichalcogenides
journal, June 1984
- Kertesz, Miklos; Hoffmann, Roald
- Journal of the American Chemical Society, Vol. 106, Issue 12
Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006
- Lewis, N. S.; Nocera, D. G.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
Molybdenum Speciation and its Impact on Catalytic Activity during Methane Dehydroaromatization in Zeolite ZSM-5 as Revealed by Operando X-Ray Methods
journal, March 2016
- Lezcano-González, Inés; Oord, Ramon; Rovezzi, Mauro
- Angewandte Chemie International Edition, Vol. 55, Issue 17
Sub-5 nm Ultra-Fine FeP Nanodots as Efficient Co-Catalysts Modified Porous g-C 3 N 4 for Precious-Metal-Free Photocatalytic Hydrogen Evolution under Visible Light
journal, January 2019
- Zeng, Deqian; Zhou, Ting; Ong, Wee-Jun
- ACS Applied Materials & Interfaces, Vol. 11, Issue 6
Toward Inexpensive Photocatalytic Hydrogen Evolution: A Nickel Sulfide Catalyst Supported on a High-Stability Metal–Organic Framework
journal, August 2016
- Peters, Aaron W.; Li, Zhanyong; Farha, Omar K.
- ACS Applied Materials & Interfaces, Vol. 8, Issue 32
Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations
journal, October 2010
- Skúlason, Egill; Tripkovic, Vladimir; Björketun, Mårten E.
- The Journal of Physical Chemistry C, Vol. 114, Issue 42
Molybdenum Speciation and its Impact on Catalytic Activity during Methane Dehydroaromatization in Zeolite ZSM-5 as Revealed by Operando X-Ray Methods
journal, March 2016
- Lezcano-González, Inés; Oord, Ramon; Rovezzi, Mauro
- Angewandte Chemie, Vol. 128, Issue 17
Room Temperature Synthesis of an 8-Connected Zr-Based Metal–Organic Framework for Top-Down Nanoparticle Encapsulation
journal, March 2018
- Noh, Hyunho; Kung, Chung-Wei; Islamoglu, Timur
- Chemistry of Materials, Vol. 30, Issue 7
Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework
journal, January 2018
- Islamoglu, Timur; Otake, Ken-ichi; Li, Peng
- CrystEngComm, Vol. 20, Issue 39
Recent advances in heterogeneous electrocatalysts for the hydrogen evolution reaction
journal, January 2015
- Zeng, Min; Li, Yanguang
- Journal of Materials Chemistry A, Vol. 3, Issue 29
Electrochemistry of the viologens
journal, January 1981
- Bird, C. L.; Kuhn, A. T.
- Chemical Society Reviews, Vol. 10, Issue 1
Advances in the Development of Novel Cobalt Fischer−Tropsch Catalysts for Synthesis of Long-Chain Hydrocarbons and Clean Fuels
journal, May 2007
- Khodakov, Andrei Y.; Chu, Wei; Fongarland, Pascal
- Chemical Reviews, Vol. 107, Issue 5
Single-Atom-Based Vanadium Oxide Catalysts Supported on Metal–Organic Frameworks: Selective Alcohol Oxidation and Structure–Activity Relationship
journal, June 2018
- Otake, Ken-ichi; Cui, Yuexing; Buru, Cassandra T.
- Journal of the American Chemical Society, Vol. 140, Issue 28
Fine-Tuning the Activity of Metal–Organic Framework-Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane
journal, October 2017
- Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.
- Journal of the American Chemical Society, Vol. 139, Issue 42
Single-Site Cobalt Catalysts at New Zr 12 (μ 3 -O) 8 (μ 3 -OH) 8 (μ 2 -OH) 6 Metal–Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides
journal, May 2017
- Ji, Pengfei; Manna, Kuntal; Lin, Zekai
- Journal of the American Chemical Society, Vol. 139, Issue 20
Redox-Mediator-Assisted Electrocatalytic Hydrogen Evolution from Water by a Molybdenum Sulfide-Functionalized Metal–Organic Framework
journal, September 2018
- Noh, Hyunho; Kung, Chung-Wei; Otake, Ken-ichi
- ACS Catalysis, Vol. 8, Issue 10
Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework
journal, March 2018
- Peters, Aaron W.; Otake, Kenichi; Platero-Prats, Ana E.
- ACS Applied Materials & Interfaces, Vol. 10, Issue 17
Über die Realstruktur von “Ammoniakeisen” und ihre Stabilität während des Haber-Bosch-Verfahrens
journal, October 2013
- Kandemir, Timur; Schuster, Manfred E.; Senyshyn, Anatoliy
- Angewandte Chemie, Vol. 125, Issue 48
Efficient Electrocatalytic and Photoelectrochemical Hydrogen Generation Using MoS 2 and Related Compounds
journal, November 2016
- Ding, Qi; Song, Bo; Xu, Ping
- Chem, Vol. 1, Issue 5
Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks
journal, April 2019
- Otake, Ken-ichi; Ye, Jingyun; Mandal, Mukunda
- ACS Catalysis, Vol. 9, Issue 6
Single-Site Cobalt Catalysts at New Zr 8 (μ 2 -O) 8 (μ 2 -OH) 4 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles
journal, September 2016
- Ji, Pengfei; Manna, Kuntal; Lin, Zekai
- Journal of the American Chemical Society, Vol. 138, Issue 37
An Exceptionally Stable Metal–Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation
journal, October 2016
- Noh, Hyunho; Cui, Yuexing; Peters, Aaron W.
- Journal of the American Chemical Society, Vol. 138, Issue 44
Facile Dimerization of Viologen Radical Cations Covalently Bonded to β-Cyclodextrin and Suppression of the Dimerization by β-Cyclodextrin and Amphiphiles
journal, January 1996
- Park, Joon Woo; Choi, Nak Hee; Kim, Jung Ha
- The Journal of Physical Chemistry, Vol. 100, Issue 2
Pushing the Limits on Metal–Organic Frameworks as a Catalyst Support: NU-1000 Supported Tungsten Catalysts for o -Xylene Isomerization and Disproportionation
journal, June 2018
- Ahn, Sol; Nauert, Scott L.; Buru, Cassandra T.
- Journal of the American Chemical Society, Vol. 140, Issue 27
Topology and porosity control of metal–organic frameworks through linker functionalization
journal, January 2019
- Lyu, Jiafei; Zhang, Xuan; Otake, Ken-ichi
- Chemical Science, Vol. 10, Issue 4
Structure of intrazeolite molybdenum oxide clusters and their catalysis of the oxidation of ethyl alcohol
journal, May 2002
- Okamoto, Yasuaki; Oshima, Nobuyuki; Kobayashi, Yasuhiro
- Physical Chemistry Chemical Physics, Vol. 4, Issue 12
How a century of ammonia synthesis changed the world
journal, September 2008
- Erisman, Jan Willem; Sutton, Mark A.; Galloway, James
- Nature Geoscience, Vol. 1, Issue 10
P ROSPECTS FOR B UILDING A H YDROGEN E NERGY I NFRASTRUCTURE
journal, November 1999
- Ogden, Joan M.
- Annual Review of Energy and the Environment, Vol. 24, Issue 1
Catalyzing the Hydrogen Evolution Reaction (HER) with Molybdenum Sulfide Nanomaterials
journal, October 2014
- Benck, Jesse D.; Hellstern, Thomas R.; Kibsgaard, Jakob
- ACS Catalysis, Vol. 4, Issue 11
Defining the Proton Topology of the Zr6-Based Metal–Organic Framework NU-1000
journal, October 2014
- Planas, Nora; Mondloch, Joseph E.; Tussupbayev, Samat
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 21, p. 3716-3723
Molybdenum Sulfide within a Metal–Organic Framework for Photocatalytic Hydrogen Evolution from Water
journal, January 2019
- Noh, Hyunho; Yang, Ying; Ahn, Sol
- Journal of The Electrochemical Society, Vol. 166, Issue 5
Noble metal-free hydrogen evolution catalysts for water splitting
journal, January 2015
- Zou, Xiaoxin; Zhang, Yu
- Chemical Society Reviews, Vol. 44, Issue 15
A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production
journal, April 2007
- Ni, Meng; Leung, Michael K. H.; Leung, Dennis Y. C.
- Renewable and Sustainable Energy Reviews, Vol. 11, Issue 3
A review of advanced catalyst development for Fischer–Tropsch synthesis of hydrocarbons from biomass derived syn-gas
journal, January 2014
- Jahangiri, Hessam; Bennett, James; Mahjoubi, Parvin
- Catal. Sci. Technol., Vol. 4, Issue 8
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis
journal, June 2012
- Costentin, Cyrille; Drouet, Samuel; Robert, Marc
- Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242
Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts
journal, July 2007
- Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J.
- Science, Vol. 317, Issue 5834, p. 100-102
Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
journal, May 2013
- Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David
- Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297
Amorphous Molybdenum Sulfide Catalysts for Electrochemical Hydrogen Production: Insights into the Origin of their Catalytic Activity
journal, August 2012
- Benck, Jesse D.; Chen, Zhebo; Kuritzky, Leah Y.
- ACS Catalysis, Vol. 2, Issue 9, p. 1916-1923
Interrogating Kinetic versus Thermodynamic Topologies of Metal–Organic Frameworks via Combined Transmission Electron Microscopy and X-ray Diffraction Analysis
journal, March 2019
- Gong, Xinyi; Noh, Hyunho; Gianneschi, Nathan C.
- Journal of the American Chemical Society, Vol. 141, Issue 15
The Haber-Bosch Process Revisited: On the Real Structure and Stability of “Ammonia Iron” under Working Conditions
journal, October 2013
- Kandemir, Timur; Schuster, Manfred E.; Senyshyn, Anatoliy
- Angewandte Chemie International Edition, Vol. 52, Issue 48
Active edge sites in MoSe 2 and WSe 2 catalysts for the hydrogen evolution reaction: a density functional study
journal, January 2014
- Tsai, Charlie; Chan, Karen; Abild-Pedersen, Frank
- Phys. Chem. Chem. Phys., Vol. 16, Issue 26