Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst

Chen, Yongwei; Zhang, Xuan; Wang, Xingjie; Drout, Riki J.; Mian, Mohammad Rasel; Cao, Ran; Ma, Kaikai; Xia, Qibin; Li, Zhong; Farha, Omar K.

doi:10.1021/jacs.0c12963

Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst

Journal Article · Wed Mar 10 23:00:00 EST 2021 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c12963· OSTI ID:1777839

^[1]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[3]; ^[3]; ^[2]

South China Univ. of Technology, Guangdong (China); Northwestern Univ., Evanston, IL (United States); University of Minnesota
Northwestern Univ., Evanston, IL (United States)
South China Univ. of Technology, Guangdong (China)

The understanding of structure–activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species’ structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr₆ node of a mesoporous zirconium-based metal–organic framework (MOF) NU-1200, using solvothermal deposition in MOFs (SIM). Due to the high crystallinity of the NU-1200 support, the precise structure of the resulting molybdenum catalyst, Mo-NU-1200, was characterized through single-crystal X-ray diffraction (SCXRD). Two distinct anchoring modes of the molybdenum species were observed: one mode (Mo1), displaying an octahedral geometry, coordinated to the node through one terminal oxygen atom and the other mode (Mo2) coordinated to two adjacent Zr₆ node oxygen atoms in a tetrahedral geometry. To investigate the role of base in the catalytic activity of these Mo centers, we assessed the activity of Mo-NU-1200 for the aerobic oxidation of 4-methoxybenzyl alcohol as a model reaction. The results revealed that Mo-NU-1200 exhibited remarkably higher catalytic reactivity under base-free conditions, while the presence of base inhibited the catalytic reactivity of this species. SCXRD studies revealed that the molybdenum binding motifs (structures of the supported metal on the Zr₆ node in the MOF) changed over the course of the reactions. Following the oxidation without base, both pristine coordination modes (Mo1 and Mo2) evolved into a new coordination mode (Mo3), in which the molybdenum atom coordinated to two adjacent oxygen atoms from the Zr₆ node in an octahedral geometry, while in the presence of base, the pristine Mo1 coordination mode evolved entirely into the pristine Mo2. Here, this study demonstrates the direct observation of an active species’ structural evolution from metal installation to subsequent catalytic reaction. As a result, these subtle structural changes in catalyst binding motifs led to distinct differences in catalytic activities, providing a compelling strategy for elucidating structure–activity relationships.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); NSF

Grant/Contract Number:: SC0012702

OSTI ID:: 1777839

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 143; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

Pore Chemistry of Metal–Organic Frameworks Ji, Zhe; Wang, Haoze; Canossa, Stefano Advanced Functional Materials, Vol. 30, Issue 41 https://doi.org/10.1002/adfm.202000238	journal	May 2020
Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties Krause, Simon; Hosono, Nobuhiko; Kitagawa, Susumu Angewandte Chemie International Edition, Vol. 59, Issue 36 https://doi.org/10.1002/anie.202004535	journal	August 2020
CO ₂ Methanation via Amino Alcohol Relay Molecules Employing a Ruthenium Nanoparticle/Metal Organic Framework Catalyst Cui, Xinjiang; Shyshkanov, Serhii; Nguyen, Tu N. Angewandte Chemie International Edition, Vol. 59, Issue 38 https://doi.org/10.1002/anie.202004618	journal	July 2020
A Biomimetic Pathway for Vanadium-Catalyzed Aerobic Oxidation of Alcohols: Evidence for a Base-Assisted Dehydrogenation Mechanism Wigington, Bethany N.; Drummond, Michael L.; Cundari, Thomas R. Chemistry - A European Journal, Vol. 18, Issue 47 https://doi.org/10.1002/chem.201202499	journal	October 2012
Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation : Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation Liu, Tian-Fu; Vermeulen, Nicolaas A.; Howarth, Ashlee J. European Journal of Inorganic Chemistry, Vol. 2016, Issue 27 https://doi.org/10.1002/ejic.201600627	journal	July 2016
Influence of the host oxide of sulfated-titania catalysts on partial oxidation methanol reaction Zhao, Hongying; Bennici, Simona; Shen, Jianyi Applied Catalysis A: General, Vol. 385, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.07.017	journal	September 2010
Metal–organic frameworks: A tunable platform to access single-site heterogeneous catalysts Wasson, Megan C.; Buru, Cassandra T.; Chen, Zhijie Applied Catalysis A: General, Vol. 586 https://doi.org/10.1016/j.apcata.2019.117214	journal	September 2019
Topology Meets Reticular Chemistry for Chemical Separations: MOFs as a Case Study Bhatt, Prashant M.; Guillerm, Vincent; Datta, Shuvo Jit Chem, Vol. 6, Issue 7 https://doi.org/10.1016/j.chempr.2020.06.018	journal	July 2020
Digital Reticular Chemistry Lyu, Hao; Ji, Zhe; Wuttke, Stefan Chem, Vol. 6, Issue 9 https://doi.org/10.1016/j.chempr.2020.08.008	journal	September 2020
Lewis acid property and catalytic performance of MoO3/SiO2 for propylene epoxidation by CHP: Effects of precipitant pH value and rare earth additive Shen, Kai; Liu, Xiaohui; Lu, Guanzhong Journal of Molecular Catalysis A: Chemical, Vol. 373 https://doi.org/10.1016/j.molcata.2013.02.020	journal	July 2013
Postsynthetic Oxidation of the Coordination Site in a Heterometallic Metal–Organic Framework: Tuning Catalytic Behaviors Han, Yi; Sinnwell, Michael A.; Surbella, Robert G. Chemistry of Materials, Vol. 32, Issue 12 https://doi.org/10.1021/acs.chemmater.0c01267	journal	May 2020
Atomically Dispersed Metals on Well-Defined Supports including Zeolites and Metal–Organic Frameworks: Structure, Bonding, Reactivity, and Catalysis Babucci, Melike; Guntida, Adisak; Gates, Bruce C. Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.0c00864	journal	October 2020
State of the Art and Prospects in Metal–Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis Wang, Qi; Astruc, Didier Chemical Reviews, Vol. 120, Issue 2 https://doi.org/10.1021/acs.chemrev.9b00223	journal	June 2019
Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives Bavykina, Anastasiya; Kolobov, Nikita; Khan, Il Son Chemical Reviews, Vol. 120, Issue 16 https://doi.org/10.1021/acs.chemrev.9b00685	journal	March 2020
Metal–Organic Framework-Based Catalysts with Single Metal Sites Wei, Yong-Sheng; Zhang, Mei; Zou, Ruqiang Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.9b00757	journal	May 2020
Chemical Synthesis of Single Atomic Site Catalysts Ji, Shufang; Chen, Yuanjun; Wang, Xiaolu Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.9b00818	journal	April 2020
Molybdenum Oxide, Oxycarbide, and Carbide: Controlling the Dynamic Composition, Size, and Catalytic Activity of Zeolite-Supported Nanostructures Zheng, Yiteng; Tang, Yadan; Gallagher, James R. The Journal of Physical Chemistry C, Vol. 123, Issue 36 https://doi.org/10.1021/acs.jpcc.9b05449	journal	August 2019
Copper Nanocrystals Encapsulated in Zr-based Metal–Organic Frameworks for Highly Selective CO ₂ Hydrogenation to Methanol Rungtaweevoranit, Bunyarat; Baek, Jayeon; Araujo, Joyce R. Nano Letters, Vol. 16, Issue 12 https://doi.org/10.1021/acs.nanolett.6b03637	journal	November 2016
Strategies for Incorporating Catalytically Active Polyoxometalates in Metal–Organic Frameworks for Organic Transformations Buru, Cassandra T.; Farha, Omar K. ACS Applied Materials & Interfaces, Vol. 12, Issue 5 https://doi.org/10.1021/acsami.9b19785	journal	January 2020
Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation Wang, Xingjie; Zhang, Xuan; Pandharkar, Riddhish ACS Catalysis, Vol. 10, Issue 16 https://doi.org/10.1021/acscatal.0c01844	journal	July 2020
Single-Atom Ru-Implanted Metal–Organic Framework/MnO ₂ for the Highly Selective Oxidation of NO _x by Plasma Activation Chen, Si; Zhou, Yi; Li, Jieyuan ACS Catalysis, Vol. 10, Issue 17 https://doi.org/10.1021/acscatal.0c02001	journal	August 2020
Combining Benzyl Alcohol Oxidation Saturation Kinetics and Hammett Studies as Mechanistic Tools for Examining Supported Metal Catalysts Mahdavi-Shakib, Akbar; Sempel, Janine; Babb, Lauren ACS Catalysis, Vol. 10, Issue 17 https://doi.org/10.1021/acscatal.0c02212	journal	August 2020
Cerium(IV) Enhances the Catalytic Oxidation Activity of Single-Site Cu Active Sites in MOFs He, Xin; Looker, Benjamin G.; Dinh, Kimberly T. ACS Catalysis, Vol. 10, Issue 14 https://doi.org/10.1021/acscatal.0c02493	journal	June 2020
Controlled Deposition of Silica on Titania-Silica to Alter the Active Site Surroundings on Epoxidation Catalysts Ardagh, M. Alexander; Bregante, Daniel T.; Flaherty, David W. ACS Catalysis, Vol. 10, Issue 21 https://doi.org/10.1021/acscatal.0c02937	journal	October 2020
Metal–Organic Framework Nodes as a Supporting Platform for Tailoring the Activity of Metal Catalysts Syed, Zoha H.; Sha, Fanrui; Zhang, Xuan ACS Catalysis, Vol. 10, Issue 19 https://doi.org/10.1021/acscatal.0c03056	journal	September 2020
Size Dependence of Pt Catalysts for Propane Dehydrogenation: from Atomically Dispersed to Nanoparticles Zhang, Wei; Wang, Haizhi; Jiang, Jiawei ACS Catalysis, Vol. 10, Issue 21 https://doi.org/10.1021/acscatal.0c03286	journal	October 2020
Bruce Gates: A Career in Catalysis Cooper, Cawas; Dooley, Kerry M.; Fierro-Gonzalez, Juan C. ACS Catalysis, Vol. 10, Issue 20 https://doi.org/10.1021/acscatal.0c03568	journal	September 2020
Spectroscopic and Computational Study of Cr Oxide Structures and Their Anchoring Sites on ZSM-5 Zeolites Gao, Jie; Zheng, Yiteng; Tang, Yadan ACS Catalysis, Vol. 5, Issue 5 https://doi.org/10.1021/acscatal.5b00333	journal	March 2015
Catalytic Zirconium/Hafnium-Based Metal–Organic Frameworks Rimoldi, Martino; Howarth, Ashlee J.; DeStefano, Matthew R. ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b02923	journal	December 2016
Redox-Mediator-Assisted Electrocatalytic Hydrogen Evolution from Water by a Molybdenum Sulfide-Functionalized Metal–Organic Framework Noh, Hyunho; Kung, Chung-Wei; Otake, Ken-ichi ACS Catalysis, Vol. 8, Issue 10 https://doi.org/10.1021/acscatal.8b02921	journal	September 2018
Enhanced Activity of Heterogeneous Pd(II) Catalysts on Acid-Functionalized Metal–Organic Frameworks Otake, Ken-ichi; Ye, Jingyun; Mandal, Mukunda ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b01043	journal	April 2019
The Surface Chemistry of Metal Oxide Clusters: From Metal–Organic Frameworks to Minerals Yang, Dong; Babucci, Melike; Casey, William H. ACS Central Science, Vol. 6, Issue 9 https://doi.org/10.1021/acscentsci.0c00803	journal	August 2020
Support Effect in Oxide Catalysis: Methanol Oxidation on Vanadia/Ceria Kropp, Thomas; Paier, Joachim; Sauer, Joachim Journal of the American Chemical Society, Vol. 136, Issue 41 https://doi.org/10.1021/ja508657c	journal	October 2014
Precisely Embedding Active Sites into a Mesoporous Zr-Framework through Linker Installation for High-Efficiency Photocatalysis Pang, Jiandong; Di, Zhengyi; Qin, Jun-Sheng Journal of the American Chemical Society, Vol. 142, Issue 35 https://doi.org/10.1021/jacs.0c05758	journal	August 2020
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 Thiam, Zeynabou; Abou-Hamad, Edy; Dereli, Busra Journal of the American Chemical Society, Vol. 142, Issue 39 https://doi.org/10.1021/jacs.0c06925	journal	September 2020
Influence of Defects and H ₂ O on the Hydrogenation of CO ₂ to Methanol over Pt Nanoparticles in UiO-67 Metal–Organic Framework Gutterød, Emil Sebastian; Pulumati, Sri Harsha; Kaur, Gurpreet Journal of the American Chemical Society, Vol. 142, Issue 40 https://doi.org/10.1021/jacs.0c07153	journal	September 2020
Insights into the Mechanism of n -Hexane Reforming over a Single-Site Platinum Catalyst Zhang, Shuchen; Chen, Luning; Qi, Zhiyuan Journal of the American Chemical Society, Vol. 142, Issue 39 https://doi.org/10.1021/jacs.0c07911	journal	September 2020
Node-Accessible Zirconium MOFs Lu, Zhiyong; Liu, Jian; Zhang, Xuan Journal of the American Chemical Society, Vol. 142, Issue 50 https://doi.org/10.1021/jacs.0c09782	journal	December 2020
Unexpected “Spontaneous” Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles Yang, Ying; Zhang, Xuan; Kanchanakungwankul, Siriluk Journal of the American Chemical Society, Vol. 142, Issue 50 https://doi.org/10.1021/jacs.0c10367	journal	December 2020
An Exceptionally Stable Metal–Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation Noh, Hyunho; Cui, Yuexing; Peters, Aaron W. Journal of the American Chemical Society, Vol. 138, Issue 44 https://doi.org/10.1021/jacs.6b08898	journal	October 2016
Single-Atom-Based Vanadium Oxide Catalysts Supported on Metal–Organic Frameworks: Selective Alcohol Oxidation and Structure–Activity Relationship Otake, Ken-ichi; Cui, Yuexing; Buru, Cassandra T. Journal of the American Chemical Society, Vol. 140, Issue 28 https://doi.org/10.1021/jacs.8b05107	journal	June 2018
Highly Active and Stable Single-Atom Cu Catalysts Supported by a Metal–Organic Framework Abdel-Mageed, Ali M.; Rungtaweevoranit, Bunyarat; Parlinska-Wojtan, Magdalena Journal of the American Chemical Society, Vol. 141, Issue 13 https://doi.org/10.1021/jacs.8b11386	journal	March 2019
Bioinspired Metal–Organic Framework Catalysts for Selective Methane Oxidation to Methanol Baek, Jayeon; Rungtaweevoranit, Bunyarat; Pei, Xiaokun Journal of the American Chemical Society, Vol. 140, Issue 51 https://doi.org/10.1021/jacs.8b11525	journal	December 2018
Vanadium Catalyst on Isostructural Transition Metal, Lanthanide, and Actinide Based Metal–Organic Frameworks for Alcohol Oxidation Wang, Xingjie; Zhang, Xuan; Li, Peng Journal of the American Chemical Society https://doi.org/10.1021/jacs.9b02603	journal	May 2019
Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic Framework Zheng, Jian; Ye, Jingyun; Ortuño, Manuel A. Journal of the American Chemical Society, Vol. 141, Issue 23 https://doi.org/10.1021/jacs.9b02902	journal	May 2019
Crystallographic Visualization of Postsynthetic Nickel Clusters into Metal–Organic Framework Wang, Xiao-Ning; Zhang, Peng; Kirchon, Angelo Journal of the American Chemical Society, Vol. 141, Issue 34 https://doi.org/10.1021/jacs.9b06711	journal	August 2019
Defining the Proton Topology of the Zr₆-Based Metal–Organic Framework NU-1000 Planas, Nora; Mondloch, Joseph E.; Tussupbayev, Samat The Journal of Physical Chemistry Letters, Vol. 5, Issue 21, p. 3716-3723 https://doi.org/10.1021/jz501899j	journal	October 2014
Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias Nature Materials, Vol. 16, Issue 9 https://doi.org/10.1038/nmat4938	journal	July 2017
Structural transformation of highly active metal–organic framework electrocatalysts during the oxygen evolution reaction Zhao, Shenlong; Tan, Chunhui; He, Chun-Ting Nature Energy, Vol. 5, Issue 11 https://doi.org/10.1038/s41560-020-00709-1	journal	October 2020
Boosting the photoreduction activity of Cr( vi ) in metal–organic frameworks by photosensitiser incorporation and framework ionization Zheng, He-Qi; He, Xing-Hao; Zeng, Yong-Nian Journal of Materials Chemistry A, Vol. 8, Issue 33 https://doi.org/10.1039/C9TA13339A	journal	January 2020
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 Sousa, Sara C. A.; Cabrita, Ivânia; Fernandes, Ana C. Chemical Society Reviews, Vol. 41, Issue 17 https://doi.org/10.1039/c2cs35155b	journal	January 2012
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
Identification of molybdenum oxide nanostructures on zeolites for natural gas conversion Gao, J.; Zheng, Y.; Jehng, J. -M. Science, Vol. 348, Issue 6235 https://doi.org/10.1126/science.aaa7048	journal	April 2015

Similar Records

Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation

Journal Article · Thu Feb 17 23:00:00 EST 2022 · Journal of the American Chemical Society · OSTI ID:1870852

Insights into the Structure–Activity Relationships in Metal–Organic Framework-Supported Nickel Catalysts for Ethylene Hydrogenation

Journal Article · Thu Jul 30 00:00:00 EDT 2020 · ACS Catalysis · OSTI ID:1721720

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Catalysts
Crystal structure
Metal organic frameworks
Molybdenum
Oxidation reactions

CCDC 2041641: Experimental Crystal Structure Determination Yongwei, Chen,; Xuan, Zhang,; Xingjie, Wang, https://doi.org/10.5517/ccdc.csd.cc26jhdn The current record is supplemented by this dataset	dataset	January 2021
CCDC 2041642: Experimental Crystal Structure Determination Yongwei, Chen,; Xuan, Zhang,; Xingjie, Wang, https://doi.org/10.5517/ccdc.csd.cc26jhfp The current record is supplemented by this dataset	dataset	January 2021
CCDC 2041649: Experimental Crystal Structure Determination Yongwei, Chen,; Xuan, Zhang,; Xingjie, Wang, https://doi.org/10.5517/ccdc.csd.cc26jhnx The current record is supplemented by this dataset	dataset	January 2021

Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst

Citation Formats

References (53)

Linked Research (3)

Similar Records

Related Subjects