Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation
Abstract
Solid supports are crucial in heterogeneous catalysis due to their profound effects on catalytic activity and selectivity. However, elucidating the specific effects arising from such supports remains challenging. We selected a series of metal–organic frameworks (MOFs) with 8-connected Zr6 nodes as supports to deposit molybdenum(VI) onto to study the effects of pore environment and topology on the resulting Mo-supported catalysts. As characterized by X-ray absorption spectroscopy (XAS) and single-crystal X-ray diffraction (SCXRD), we modulated the chemical environments of the deposited Mo species. For Mo-NU-1000, the Mo species monodentately bound to the Zr6 nodes were anchored in the microporous c-pore, but for Mo-NU-1008 they were bound in the mesopore of Mo-NU-1008. Both monodentate and bidentate modes were found in the mesopore of Mo-NU-1200. Cyclohexene epoxidation with H2O2 was probed to evaluate the support effect on catalytic activity and to unveil the resulting structure–activity relationships. SCXRD and XAS studies demonstrated the atomically precise structural differences of the Mo binding motifs over the course of cyclohexene epoxidation. No apparent structural change was observed for Mo-NU-1000, whereas the monodentate mode of Mo species in Mo-NU-1008 and the monodentate and bidentate Mo species in Mo-NU-1200 evolved to a new bidentate mode bound between two adjacentmore »
- Authors:
-
[1];
[2];
[2];
[2];
[3];
[2];
[2];
[2];
[2];
[2]
- Qingdao Univ. of Science and Technology (China); Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); USDoD
- OSTI Identifier:
- 1870852
- Grant/Contract Number:
- FG02-03ER15457; 22108141
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 8; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Catalysts; Mathematical methods; Metal organic frameworks; Organic reactions; Selectivity
Citation Formats
Chen, Yongwei, Ahn, Sol, Mian, Mohammad Rasel, Wang, Xingjie, Ma, Qing, Son, Florencia A., Yang, Lifeng, Ma, Kaikai, Zhang, Xuan, Notestein, Justin M., and Farha, Omar K. Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation. United States: N. p., 2022.
Web. doi:10.1021/jacs.1c12421.
Chen, Yongwei, Ahn, Sol, Mian, Mohammad Rasel, Wang, Xingjie, Ma, Qing, Son, Florencia A., Yang, Lifeng, Ma, Kaikai, Zhang, Xuan, Notestein, Justin M., & Farha, Omar K. Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation. United States. https://doi.org/10.1021/jacs.1c12421
Chen, Yongwei, Ahn, Sol, Mian, Mohammad Rasel, Wang, Xingjie, Ma, Qing, Son, Florencia A., Yang, Lifeng, Ma, Kaikai, Zhang, Xuan, Notestein, Justin M., and Farha, Omar K. Fri .
"Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation". United States. https://doi.org/10.1021/jacs.1c12421. https://www.osti.gov/servlets/purl/1870852.
@article{osti_1870852,
title = {Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation},
author = {Chen, Yongwei and Ahn, Sol and Mian, Mohammad Rasel and Wang, Xingjie and Ma, Qing and Son, Florencia A. and Yang, Lifeng and Ma, Kaikai and Zhang, Xuan and Notestein, Justin M. and Farha, Omar K.},
abstractNote = {Solid supports are crucial in heterogeneous catalysis due to their profound effects on catalytic activity and selectivity. However, elucidating the specific effects arising from such supports remains challenging. We selected a series of metal–organic frameworks (MOFs) with 8-connected Zr6 nodes as supports to deposit molybdenum(VI) onto to study the effects of pore environment and topology on the resulting Mo-supported catalysts. As characterized by X-ray absorption spectroscopy (XAS) and single-crystal X-ray diffraction (SCXRD), we modulated the chemical environments of the deposited Mo species. For Mo-NU-1000, the Mo species monodentately bound to the Zr6 nodes were anchored in the microporous c-pore, but for Mo-NU-1008 they were bound in the mesopore of Mo-NU-1008. Both monodentate and bidentate modes were found in the mesopore of Mo-NU-1200. Cyclohexene epoxidation with H2O2 was probed to evaluate the support effect on catalytic activity and to unveil the resulting structure–activity relationships. SCXRD and XAS studies demonstrated the atomically precise structural differences of the Mo binding motifs over the course of cyclohexene epoxidation. No apparent structural change was observed for Mo-NU-1000, whereas the monodentate mode of Mo species in Mo-NU-1008 and the monodentate and bidentate Mo species in Mo-NU-1200 evolved to a new bidentate mode bound between two adjacent oxygen atoms from the Zr6 node. This work demonstrates the great advantage of using MOF supports for constructing heterogeneous catalysts with modulated chemical environments of an active species and elucidating structure–activity relationships in the resulting reactions.},
doi = {10.1021/jacs.1c12421},
journal = {Journal of the American Chemical Society},
number = 8,
volume = 144,
place = {United States},
year = {Fri Feb 18 00:00:00 EST 2022},
month = {Fri Feb 18 00:00:00 EST 2022}
}
Free Publicly Available Full Text
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:
Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst
journal, March 2021
- Chen, Yongwei; Zhang, Xuan; Wang, Xingjie
- Journal of the American Chemical Society, Vol. 143, Issue 11
Metal–Organic Framework-Based Hierarchically Porous Materials: Synthesis and Applications
journal, July 2021
- Cai, Guorui; Yan, Peng; Zhang, Liangliang
- Chemical Reviews, Vol. 121, Issue 20
Isomerization and Selective Hydrogenation of Propyne: Screening of Metal–Organic Frameworks Modified by Atomic Layer Deposition
journal, November 2020
- Hackler, Ryan A.; Pandharkar, Riddhish; Ferrandon, Magali S.
- Journal of the American Chemical Society, Vol. 142, Issue 48
Demonstrating the Critical Role of Solvation in Supported Ti and Nb Epoxidation Catalysts via Vapor-Phase Kinetics
journal, January 2020
- Ahn, Sol; Nauert, Scott L.; Hicks, Kenton E.
- ACS Catalysis, Vol. 10, Issue 4
Insights into the Mechanism of n -Hexane Reforming over a Single-Site Platinum Catalyst
journal, September 2020
- Zhang, Shuchen; Chen, Luning; Qi, Zhiyuan
- Journal of the American Chemical Society, Vol. 142, Issue 39
Highly Active Heterogeneous Catalyst for Ethylene Dimerization Prepared by Selectively Doping Ni on the Surface of a Zeolitic Imidazolate Framework
journal, April 2021
- Chen, Cailing; Alalouni, Mohammed R.; Dong, Xinglong
- Journal of the American Chemical Society, Vol. 143, Issue 18
Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives
journal, March 2020
- Bavykina, Anastasiya; Kolobov, Nikita; Khan, Il Son
- Chemical Reviews, Vol. 120, Issue 16
Extension of Surface Organometallic Chemistry to Metal–Organic Frameworks: Development of a Well-Defined Single Site [(≡Zr–O−)W(═O)(CH 2 t Bu) 3 ] Olefin Metathesis Catalyst
journal, September 2020
- Thiam, Zeynabou; Abou-Hamad, Edy; Dereli, Busra
- Journal of the American Chemical Society, Vol. 142, Issue 39
Tandem In 2 O 3 -Pt/Al 2 O 3 catalyst for coupling of propane dehydrogenation to selective H 2 combustion
journal, March 2021
- Yan, Huan; He, Kun; Samek, Izabela A.
- Science, Vol. 371, Issue 6535
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
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
Vanadium Catalyst on Isostructural Transition Metal, Lanthanide, and Actinide Based Metal–Organic Frameworks for Alcohol Oxidation
journal, May 2019
- Wang, Xingjie; Zhang, Xuan; Li, Peng
- Journal of the American Chemical Society
Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal–Organic Frameworks
journal, January 2021
- Otake, Ken-ichi; Ahn, Sol; Knapp, Julia
- Inorganic Chemistry, Vol. 60, Issue 4
Pore Chemistry of Metal–Organic Frameworks
journal, May 2020
- Ji, Zhe; Wang, Haoze; Canossa, Stefano
- Advanced Functional Materials, Vol. 30, Issue 41
Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic Framework
journal, May 2019
- Zheng, Jian; Ye, Jingyun; Ortuño, Manuel A.
- Journal of the American Chemical Society, Vol. 141, Issue 23
Introducing Nonstructural Ligands to Zirconia-like Metal–Organic Framework Nodes To Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation
journal, March 2019
- Liu, Jian; Li, Zhanyong; Zhang, Xuan
- ACS Catalysis, Vol. 9, Issue 4
Stable Metal–Organic Framework-Supported Niobium Catalysts
journal, October 2016
- Ahn, Sol; Thornburg, Nicholas E.; Li, Zhanyong
- Inorganic Chemistry, Vol. 55, Issue 22
Support Effect in High Activity Gold Catalysts for CO Oxidation
journal, January 2006
- Comotti, Massimiliano; Li, Wen-Cui; Spliethoff, Bernd
- Journal of the American Chemical Society, Vol. 128, Issue 3
Unexpected “Spontaneous” Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles
journal, December 2020
- Yang, Ying; Zhang, Xuan; Kanchanakungwankul, Siriluk
- Journal of the American Chemical Society, Vol. 142, Issue 50
Reticular synthesis and the design of new materials
journal, June 2003
- Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
- Nature, Vol. 423, Issue 6941, p. 705-714
Structural Diversity of Zirconium Metal–Organic Frameworks and Effect on Adsorption of Toxic Chemicals
journal, December 2020
- Chen, Yongwei; Zhang, Xuan; Mian, Mohammad Rasel
- Journal of the American Chemical Society, Vol. 142, Issue 51
High-valent oxo-molybdenum and oxo-rhenium complexes as efficient catalysts for X–H (X = Si, B, P and H) bond activation and for organic reductions
journal, January 2012
- Sousa, Sara C. A.; Cabrita, Ivânia; Fernandes, Ana C.
- Chemical Society Reviews, Vol. 41, Issue 17
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
Metal–organic frameworks as catalytic selectivity regulators for organic transformations
journal, January 2021
- Guo, Jun; Qin, Yutian; Zhu, Yanfei
- Chemical Society Reviews, Vol. 50, Issue 9
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
Digital Reticular Chemistry
journal, September 2020
- Lyu, Hao; Ji, Zhe; Wuttke, Stefan
- Chem, Vol. 6, Issue 9
Bruce Gates: A Career in Catalysis
journal, September 2020
- Cooper, Cawas; Dooley, Kerry M.; Fierro-Gonzalez, Juan C.
- ACS Catalysis, Vol. 10, Issue 20
Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation
journal, July 2020
- Wang, Xingjie; Zhang, Xuan; Pandharkar, Riddhish
- ACS Catalysis, Vol. 10, Issue 16
Cyclohexene epoxidation with H 2 O 2 in the vapor and liquid phases over a vanadium-based metal–organic framework
journal, January 2020
- Yoon, Tae-Ung; Ahn, Sol; Kim, Ah-Reum
- Catalysis Science & Technology, Vol. 10, Issue 14
Size Dependence of Pt Catalysts for Propane Dehydrogenation: from Atomically Dispersed to Nanoparticles
journal, October 2020
- Zhang, Wei; Wang, Haizhi; Jiang, Jiawei
- ACS Catalysis, Vol. 10, Issue 21
Reticular chemistry approach to explore the catalytic CO2-epoxide cycloaddition reaction over tetrahedral coordination Lewis acidic sites in a Rutile-type Zinc-phosphonocarboxylate framework
journal, January 2022
- Kong, Lingtao; Li, Zhouxun; Hu, Han
- Chemical Engineering Journal, Vol. 427
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
Cerium(IV) Enhances the Catalytic Oxidation Activity of Single-Site Cu Active Sites in MOFs
journal, June 2020
- He, Xin; Looker, Benjamin G.; Dinh, Kimberly T.
- ACS Catalysis, Vol. 10, Issue 14
Modulating Coordination Environment of Single-Atom Catalysts and Their Proximity to Photosensitive Units for Boosting MOF Photocatalysis
journal, July 2021
- Ma, Xing; Liu, Hang; Yang, Weijie
- Journal of the American Chemical Society, Vol. 143, Issue 31
Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion
journal, April 2015
- Gao, J.; Zheng, Y.; Jehng, J. -M.
- Science, Vol. 348, Issue 6235
Crystallographic Visualization of Postsynthetic Nickel Clusters into Metal–Organic Framework
journal, August 2019
- Wang, Xiao-Ning; Zhang, Peng; Kirchon, Angelo
- Journal of the American Chemical Society, Vol. 141, Issue 34
Cerium-Based Metal–Organic Layers Catalyze Hydrogen Evolution Reaction through Dual Photoexcitation
journal, March 2020
- Song, Yang; Pi, Yunhong; Feng, Xuanyu
- Journal of the American Chemical Society, Vol. 142, Issue 15
The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013
- Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
- Science, Vol. 341, Issue 6149, p. 1230444-1230444
Crystal Plane Effect of Ceria on Supported Copper Oxide Cluster Catalyst for CO Oxidation: Importance of Metal–Support Interaction
journal, January 2017
- Wang, Wei-Wei; Yu, Wen-Zhu; Du, Pei-Pei
- ACS Catalysis, Vol. 7, Issue 2
In Situ Implanting of Single Tungsten Sites into Defective UiO‐66(Zr) by Solvent‐Free Route for Efficient Oxidative Desulfurization at Room Temperature
journal, July 2021
- Ye, Gan; Wang, Hanlu; Chen, Wenxing
- Angewandte Chemie International Edition, Vol. 60, Issue 37
Periodic Trends in Highly Dispersed Groups IV and V Supported Metal Oxide Catalysts for Alkene Epoxidation with H 2 O 2
journal, August 2015
- Thornburg, Nicholas E.; Thompson, Anthony B.; Notestein, Justin M.
- ACS Catalysis, Vol. 5, Issue 9
Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts
journal, July 2013
- Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R.
- Science, Vol. 341, Issue 6147