Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons

Khoo, Rebecca Shu Hui; Fiankor, Christian; Yang, Sizhuo; Hu, Wenhui; Yang, Chongqing; Lu, Jingzhi; Morton, Martha D.; Zhang, Xu; Liu, Yi; Huang, Jier; Zhang, Jian

doi:10.1021/jacs.3c07237

Title: Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons

Journal Article · Wed Oct 25 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c07237· OSTI ID:2203780

Khoo, Rebecca Shu Hui ^[1];

^[2]; Yang, Sizhuo ^[1]; Hu, Wenhui ^[3]; Yang, Chongqing ^[1];

^[2];

^[2]; Zhang, Xu ^[4];

^[1];

^[3];

^[5]

The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Department of Chemistry, University of Nebraska−Lincoln, Lincoln, Nebraska 68588, United States
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States
Jiangsu Engineering Laboratory for Environment Functional Materials, Jiangsu Collaborative Innovation Center of Regional Modern Agriculture & Environmental Protection, School of Chemistry and Chemical Engineering, Huaiyin Normal University, No. 111 West Changjiang Road, Huaian, Jiangsu 223300, China
The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Department of Chemistry, University of Nebraska−Lincoln, Lincoln, Nebraska 68588, United States

Heterogeneous catalysis plays an indispensable role in chemical production and energy conversion. Incorporation of transition metals into metal oxides and zeolites is a common strategy to fine-tune the activity and selectivity of the resulting solid catalysts, as either the active center or promotor. Studying the underlying mechanism is however challenging. Decorating the metal-oxo clusters with transition metals in metal–organic frameworks (MOFs) via postsynthetic modification offers a rational approach to construct well-defined structural models for better understanding of the reaction mechanism. Therefore, it is important to expand the materials scope beyond the currently widely studied zirconium MOFs consisting of Zr₆ nodes. In this work, we report the design and synthesis of a new (4,12)-connected Zr-MOF with ith topology that consists of rare Zr₉ nodes. Fe^III was further incorporated onto the Zr₉ nodes of the framework, and the resulting MOF material exhibits significantly enhanced activity and selectivity toward the photocatalytic oxidation of toluene. This work demonstrates a delicate ligand design strategy to control the nuclearity of Zr-oxo clusters, which further dictates the number and binding sites of transition metals and the overall photocatalytic activity toward C–H activation. Our work paves the way for future exploration of the structure–activity study of catalysts using MOFs as the model system.

View Journal Article

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 2203780

Alternate ID(s):: OSTI ID: 2205193; OSTI ID: 2328525

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 145 Journal Issue: 44; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (59)

Isomerization and Selective Hydrogenation of Propyne: Screening of Metal–Organic Frameworks Modified by Atomic Layer Deposition Hackler, Ryan A.; Pandharkar, Riddhish; Ferrandon, Magali S. Journal of the American Chemical Society, Vol. 142, Issue 48 https://doi.org/10.1021/jacs.0c08641	journal	November 2020
Recent strategies to improve the photoactivity of metal–organic frameworks Yan, Yu; Abazari, Reza; Yao, Juming Dalton Transactions, Vol. 50, Issue 7 https://doi.org/10.1039/D0DT03844J	journal	January 2021
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
Design of All-Inorganic Molecular-Based Photocatalysts Sensitive to Visible Light: Ti(IV)−O−Ce(III) Bimetallic Assemblies on Mesoporous Silica Nakamura, Ryuhei; Okamoto, Akihiro; Osawa, Hitoshi Journal of the American Chemical Society, Vol. 129, Issue 31 https://doi.org/10.1021/ja073668n	journal	August 2007
Highly Active Heterogeneous Catalyst for Ethylene Dimerization Prepared by Selectively Doping Ni on the Surface of a Zeolitic Imidazolate Framework Chen, Cailing; Alalouni, Mohammed R.; Dong, Xinglong Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c02272	journal	April 2021
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 Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature Li, Zhanyong; Peters, Aaron W.; Bernales, Varinia ACS Central Science, Vol. 3, Issue 1 https://doi.org/10.1021/acscentsci.6b00290	journal	November 2016
Symmetry-Guided Synthesis of N,N′-Bicarbazole and Porphyrin-Based Mixed-Ligand Metal–Organic Frameworks: Light Harvesting and Energy Transfer Fiankor, Christian; Nyakuchena, James; Khoo, Rebecca Shu Hui Journal of the American Chemical Society, Vol. 143, Issue 48 https://doi.org/10.1021/jacs.1c10291	journal	November 2021
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
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
Vapor-Phase Cyclohexene Epoxidation by Single-Ion Fe(III) Sites in Metal–Organic Frameworks Otake, Ken-ichi; Ahn, Sol; Knapp, Julia Inorganic Chemistry, Vol. 60, Issue 4 https://doi.org/10.1021/acs.inorgchem.0c03364	journal	January 2021
Turning on Visible-Light Photocatalytic C−H Oxidation over Metal–Organic Frameworks by Introducing Metal-to-Cluster Charge Transfer Xu, Caiyun; Pan, Yating; Wan, Gang Journal of the American Chemical Society, Vol. 141, Issue 48 https://doi.org/10.1021/jacs.9b09954	journal	November 2019
Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials Cook, Timothy R.; Zheng, Yao-Rong; Stang, Peter J. Chemical Reviews, Vol. 113, Issue 1 https://doi.org/10.1021/cr3002824	journal	November 2012
Metal–Organic Frameworks (MOFs) Zhou, Hong-Cai “Joe”; Kitagawa, Susumu Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS90059F	journal	January 2014
Fe‐O Clusters Anchored on Nodes of Metal–Organic Frameworks for Direct Methane Oxidation Zhao, Wenshi; Shi, Yanan; Jiang, Yuheng Angewandte Chemie International Edition, Vol. 60, Issue 11 https://doi.org/10.1002/anie.202013807	journal	February 2021
Support Effect in High Activity Gold Catalysts for CO Oxidation Comotti, Massimiliano; Li, Wen-Cui; Spliethoff, Bernd Journal of the American Chemical Society, Vol. 128, Issue 3 https://doi.org/10.1021/ja0561441	journal	January 2006
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
Highly Specific Coordination-Driven Self-Assembly of 2D Heterometallic Metal–Organic Frameworks with Unprecedented Johnson-type (J₅₁) Nonanuclear Zr-Oxocarboxylate Clusters Gong, Wei; Arman, Hadi; Chen, Zhijie Journal of the American Chemical Society, Vol. 143, Issue 2 https://doi.org/10.1021/jacs.0c11881	journal	January 2021
Orthogonal Ternary Functionalization of a Mesoporous Metal–Organic Framework via Sequential Postsynthetic Ligand Exchange Liu, Chong; Luo, Tian-Yi; Feura, Evan S. Journal of the American Chemical Society, Vol. 137, Issue 33 https://doi.org/10.1021/jacs.5b06780	journal	August 2015
Symmetry-Guided Synthesis of Highly Porous Metal-Organic Frameworks with Fluorite Topology Zhang, Muwei; Chen, Ying-Pin; Bosch, Mathieu Angewandte Chemie International Edition, Vol. 53, Issue 3 https://doi.org/10.1002/anie.201307340	journal	November 2013
Transforming Hydroxide-Containing Metal–Organic Framework Nodes for Transition Metal Catalysis Feng, Xuanyu; Song, Yang; Lin, Wenbin Trends in Chemistry, Vol. 2, Issue 11 https://doi.org/10.1016/j.trechm.2020.08.009	journal	November 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
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
Photochemical CO ₂ Splitting by Metal-to-Metal Charge-Transfer Excitation in Mesoporous ZrCu(I)-MCM-41 Silicate Sieve Lin, Wenyong; Frei, Heinz Journal of the American Chemical Society, Vol. 127, Issue 6 https://doi.org/10.1021/ja040162l	journal	February 2005
Modulating Coordination Environment of Single-Atom Catalysts and Their Proximity to Photosensitive Units for Boosting MOF Photocatalysis Ma, Xing; Liu, Hang; Yang, Weijie Journal of the American Chemical Society, Vol. 143, Issue 31 https://doi.org/10.1021/jacs.1c05032	journal	July 2021
Vanadium-Node-Functionalized UiO-66: A Thermally Stable MOF-Supported Catalyst for the Gas-Phase Oxidative Dehydrogenation of Cyclohexene Nguyen, Huong Giang T.; Schweitzer, Neil M.; Chang, Chih-Yi ACS Catalysis, Vol. 4, Issue 8, p. 2496-2500 https://doi.org/10.1021/cs5001448	journal	June 2014
MOF-enabled confinement and related effects for chemical catalyst presentation and utilization Liu, Jian; Goetjen, Timothy A.; Wang, Qining Chemical Society Reviews, Vol. 51, Issue 3 https://doi.org/10.1039/D1CS00968K	journal	January 2022
Single-Atom Metal Oxide Sites as Traps for Charge Separation in the Zirconium-Based Metal–Organic Framework NDC–NU-1000 Kramar, Boris V.; Phelan, Brian T.; Sprague-Klein, Emily A. Energy & Fuels, Vol. 35, Issue 23 https://doi.org/10.1021/acs.energyfuels.1c02623	journal	September 2021
Topology-Based Functionalization of Robust Chiral Zr-Based Metal–Organic Frameworks for Catalytic Enantioselective Hydrogenation Jiang, Hong; Zhang, Wenqiang; Kang, Xing Journal of the American Chemical Society https://doi.org/10.1021/jacs.0c00637	journal	May 2020
[Ti ₈ Zr ₂ O ₁₂ (COO) ₁₆ ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks Yuan, Shuai; Qin, Jun-Sheng; Xu, Hai-Qun ACS Central Science, Vol. 4, Issue 1 https://doi.org/10.1021/acscentsci.7b00497	journal	November 2017
Metal–Organic Frameworks Integrate Cu Photosensitizers and Secondary Building Unit-Supported Fe Catalysts for Photocatalytic Hydrogen Evolution Pi, Yunhong; Feng, Xuanyu; Song, Yang Journal of the American Chemical Society, Vol. 142, Issue 23 https://doi.org/10.1021/jacs.0c03906	journal	May 2020
Generation and Detection of Reactive Oxygen Species in Photocatalysis Nosaka, Yoshio; Nosaka, Atsuko Y. Chemical Reviews, Vol. 117, Issue 17 https://doi.org/10.1021/acs.chemrev.7b00161	journal	August 2017
In Situ Implanting of Single Tungsten Sites into Defective UiO‐66(Zr) by Solvent‐Free Route for Efficient Oxidative Desulfurization at Room Temperature Ye, Gan; Wang, Hanlu; Chen, Wenxing Angewandte Chemie International Edition, Vol. 60, Issue 37 https://doi.org/10.1002/anie.202107018	journal	July 2021
Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng Angewandte Chemie International Edition, Vol. 54, Issue 49 https://doi.org/10.1002/anie.201505625	journal	October 2015
Reticular Chemistry in Its Chiral Form: Axially Chiral Zr(IV)-Spiro Metal–Organic Framework as a Case Study Gong, Wei; Chen, Xinfa; Fahy, Kira M. Journal of the American Chemical Society, Vol. 145, Issue 25 https://doi.org/10.1021/jacs.3c03036	journal	June 2023
Metal–Organic Frameworks in Solid–Gas Phase Catalysis Wang, Cheng; An, Bing; Lin, Wenbin ACS Catalysis, Vol. 9, Issue 1 https://doi.org/10.1021/acscatal.8b04055	journal	November 2018
Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications Islamoglu, Timur; Goswami, Subhadip; Li, Zhanyong Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00577	journal	February 2017
Zr-based metal–organic frameworks: design, synthesis, structure, and applications Bai, Yan; Dou, Yibo; Xie, Lin-Hua Chemical Society Reviews, Vol. 45, Issue 8 https://doi.org/10.1039/C5CS00837A	journal	January 2016
Cooperative copper centres in a metal–organic framework for selective conversion of CO2 to ethanol An, Bing; Li, Zhe; Song, Yang Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0308-5	journal	July 2019
Metal–Organic Frameworks for Heterogeneous Basic Catalysis Zhu, Li; Liu, Xiao-Qin; Jiang, Hai-Long Chemical Reviews, Vol. 117, Issue 12 https://doi.org/10.1021/acs.chemrev.7b00091	journal	May 2017
Catalysis and photocatalysis by metal organic frameworks Dhakshinamoorthy, Amarajothi; Li, Zhaohui; Garcia, Hermenegildo Chemical Society Reviews, Vol. 47, Issue 22 https://doi.org/10.1039/C8CS00256H	journal	January 2018
Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes Manna, Kuntal; Ji, Pengfei; Lin, Zekai Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12610	journal	August 2016
Water Adsorption in Porous Metal–Organic Frameworks and Related Materials Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381 https://doi.org/10.1021/ja500330a	journal	March 2014
Metal‐Organic Frameworks for C6 Alkane Separation Xie, Feng; Yu, Liang; Wang, Hao Angewandte Chemie International Edition, Vol. 62, Issue 20 https://doi.org/10.1002/anie.202300722	journal	March 2023
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
Tuning Zr ₆ Metal–Organic Framework (MOF) Nodes as Catalyst Supports: Site Densities and Electron-Donor Properties Influence Molecular Iridium Complexes as Ethylene Conversion Catalysts Yang, Dong; Odoh, Samuel O.; Borycz, Joshua ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b02243	journal	December 2015
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 Ji, Pengfei; Manna, Kuntal; Lin, Zekai Journal of the American Chemical Society, Vol. 138, Issue 37 https://doi.org/10.1021/jacs.6b06759	journal	September 2016
Emerging Multifunctional Metal-Organic Framework Materials Li, Bin; Wen, Hui-Min; Cui, Yuanjing Advanced Materials, Vol. 28, Issue 40 https://doi.org/10.1002/adma.201601133	journal	July 2016
Metal–Organic Framework Nodes Support Single-Site Magnesium–Alkyl Catalysts for Hydroboration and Hydroamination Reactions Manna, Kuntal; Ji, Pengfei; Greene, Francis X. Journal of the American Chemical Society, Vol. 138, Issue 24 https://doi.org/10.1021/jacs.6b03689	journal	June 2016
The Molecular Path Approaching the Active Site in Catalytic Metal–Organic Frameworks Platero-Prats, Ana E.; Mavrandonakis, Andreas; Liu, Jian Journal of the American Chemical Society, Vol. 143, Issue 48 https://doi.org/10.1021/jacs.1c11213	journal	November 2021
Reticular Chemistry: Occurrence and Taxonomy of Nets and Grammar for the Design of Frameworks Ockwig, Nathan W.; Delgado-Friedrichs, Olaf; O'Keeffe, Michael Accounts of Chemical Research, Vol. 38, Issue 3, p. 176-182 https://doi.org/10.1021/ar020022l	journal	March 2005
Single-crystal structure validation with the program PLATON Spek, A. L. Journal of Applied Crystallography, Vol. 36, Issue 1, p. 7-13 https://doi.org/10.1107/S0021889802022112	journal	January 2003
Postsynthetic Modification of Metal−Organic Frameworks for Photocatalytic Applications Lin, Huaxing; Xu, You; Wang, Bing Small Structures, Vol. 3, Issue 5 https://doi.org/10.1002/sstr.202100176	journal	February 2022
Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications Pattengale, Brian; Yang, Sizhuo; Ludwig, John Journal of the American Chemical Society, Vol. 138, Issue 26 https://doi.org/10.1021/jacs.6b04615	journal	June 2016
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
Equilibrium between hydroxyl radicals and thallium(II) and the oxidation potential of hydroxyl(aq) Schwarz, H. A.; Dodson, R. W. The Journal of Physical Chemistry, Vol. 88, Issue 16 https://doi.org/10.1021/j150660a053	journal	August 1984
Heterogeneous Catalysis Schlögl, Robert Angewandte Chemie International Edition, Vol. 54, Issue 11 https://doi.org/10.1002/anie.201410738	journal	February 2015
Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation Chen, Yongwei; Ahn, Sol; Mian, Mohammad Rasel Journal of the American Chemical Society, Vol. 144, Issue 8 https://doi.org/10.1021/jacs.1c12421	journal	February 2022
Simultaneous Control of Flexibility and Rigidity in Pore-Space-Partitioned Metal–Organic Frameworks Xiao, Yuchen; Chen, Yichong; Wang, Wei Journal of the American Chemical Society, Vol. 145, Issue 20 https://doi.org/10.1021/jacs.3c03130	journal	May 2023

Similar Records

Creating Well-Defined Hexabenzocoronene in Zirconium Metal–Organic Framework by Postsynthetic Annulation

Journal Article · Wed Jan 09 00:00:00 EST 2019 · Journal of the American Chemical Society · OSTI ID:2203780

Qin, Jun-Sheng; Yuan, Shuai; Zhang, Lei; +9 more

Zr₆O₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

Journal Article · Fri Dec 04 00:00:00 EST 2020 · ACS Catalysis · OSTI ID:2203780

Hicks, Kenton E.; Rosen, Andrew S.; Syed, Zoha H.; +3 more

Charge Transport in Zirconium-Based Metal–Organic Frameworks

Journal Article · Wed May 13 00:00:00 EDT 2020 · Accounts of Chemical Research · OSTI ID:2203780

Kung, Chung-Wei; Goswami, Subhadip; Hod, Idan; +4 more

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
aromatic compounds
hydrocarbons
ligands
mathematical methods
oxidation

Title: Postsynthetic Modification of the Nonanuclear Node in a Zirconium Metal–Organic Framework for Photocatalytic Oxidation of Hydrocarbons

Citation Formats

References (59)

Similar Records

Related Subjects