Engineering effective structural defects of metal-organic frameworks to enhance their catalytic performances

Jianjian Wang; L. M. Liu; Cailing Chen; Xinglong Dong; Qin Wang; Lujain Alfilfil; Mohammed R. Alalouni; Kexin Yao; Jianfeng Huang; Daliang Zhang; Yu Han

doi:10.1039/c9ta12230c

Engineering effective structural defects of metal-organic frameworks to enhance their catalytic performances

Jianjian Wang, L. M. Liu, Cailing Chen, Xinglong Dong, Qin Wang, Lujain Alfilfil, Mohammed R. Alalouni, Kexin Yao, Jianfeng Huang, Daliang Zhang, Yu Han

Research output: Contribution to journal › Article › peer-review

79 Scopus citations

Abstract

Metal-organic frameworks (MOFs) with a high density of metal nodes have great potential in the application of heterogeneous catalysis. However, identifying the real active site in MOF structures and tuning its amount to further improve its catalytic performance are still a great challenge. In this paper, defective UiO-66 modulated with trifluoroacetic acid (TFA) was synthesized and used for the conversion of cyclohexanone to cyclohexanol via hydrogen transfer. We found that not all structural defects were responsible for catalytic reaction, and only structural defects where open metal sites are created by a modulator were effective for cyclohexanone conversion. Then we successfully tuned the number of each type of effective structural defect (that is, missing-cluster defects or missing-linker defects) in modulated UiO-66 via precise control of the synthetic/treatment conditions. Our experimental results showed that the creation of both types of structural defects can increase the amount of effective open metal sites and then enhance their catalytic performances under the same conditions. Furthermore, the mechanism study confirmed that this reaction indeed proceeded on effective open metal sites. Our findings have further deepened the understanding of the roles of structural defects in MOF heterogeneous catalysis.

Original language	English (US)
Pages (from-to)	4464-4472
Number of pages	9
Journal	Journal of Materials Chemistry A
Volume	8
Issue number	8
DOIs	https://doi.org/10.1039/c9ta12230c
State	Published - Jan 27 2020

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: J. W. greatly acknowledges the nancial support from the National Natural Science Foundation of China (21902016) and the Fundamental Research Funds for the Central Universities (2019CDQYHG026). This research used resources of Analytical and Testing Center of Chongqing University and the Core Labs of King Abdullah University of Science and Technology. This work was dedicated to Chongqing University on the occasion of its 90th anniversary

Access to Document

10.1039/c9ta12230c

Cite this

@article{62bd20e20d0f436ca5a51ea53e0cfaff,

title = "Engineering effective structural defects of metal-organic frameworks to enhance their catalytic performances",

abstract = "Metal-organic frameworks (MOFs) with a high density of metal nodes have great potential in the application of heterogeneous catalysis. However, identifying the real active site in MOF structures and tuning its amount to further improve its catalytic performance are still a great challenge. In this paper, defective UiO-66 modulated with trifluoroacetic acid (TFA) was synthesized and used for the conversion of cyclohexanone to cyclohexanol via hydrogen transfer. We found that not all structural defects were responsible for catalytic reaction, and only structural defects where open metal sites are created by a modulator were effective for cyclohexanone conversion. Then we successfully tuned the number of each type of effective structural defect (that is, missing-cluster defects or missing-linker defects) in modulated UiO-66 via precise control of the synthetic/treatment conditions. Our experimental results showed that the creation of both types of structural defects can increase the amount of effective open metal sites and then enhance their catalytic performances under the same conditions. Furthermore, the mechanism study confirmed that this reaction indeed proceeded on effective open metal sites. Our findings have further deepened the understanding of the roles of structural defects in MOF heterogeneous catalysis.",

author = "Jianjian Wang and Liu, {L. M.} and Cailing Chen and Xinglong Dong and Qin Wang and Lujain Alfilfil and Alalouni, {Mohammed R.} and Kexin Yao and Jianfeng Huang and Daliang Zhang and Yu Han",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: J. W. greatly acknowledges the nancial support from the National Natural Science Foundation of China (21902016) and the Fundamental Research Funds for the Central Universities (2019CDQYHG026). This research used resources of Analytical and Testing Center of Chongqing University and the Core Labs of King Abdullah University of Science and Technology. This work was dedicated to Chongqing University on the occasion of its 90th anniversary",

year = "2020",

month = jan,

day = "27",

doi = "10.1039/c9ta12230c",

language = "English (US)",

volume = "8",

pages = "4464--4472",

journal = "Journal of Materials Chemistry A",

issn = "2050-7488",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

T1 - Engineering effective structural defects of metal-organic frameworks to enhance their catalytic performances

AU - Wang, Jianjian

AU - Liu, L. M.

AU - Chen, Cailing

AU - Dong, Xinglong

AU - Wang, Qin

AU - Alfilfil, Lujain

AU - Alalouni, Mohammed R.

AU - Yao, Kexin

AU - Huang, Jianfeng

AU - Zhang, Daliang

AU - Han, Yu

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: J. W. greatly acknowledges the nancial support from the National Natural Science Foundation of China (21902016) and the Fundamental Research Funds for the Central Universities (2019CDQYHG026). This research used resources of Analytical and Testing Center of Chongqing University and the Core Labs of King Abdullah University of Science and Technology. This work was dedicated to Chongqing University on the occasion of its 90th anniversary

PY - 2020/1/27

Y1 - 2020/1/27

N2 - Metal-organic frameworks (MOFs) with a high density of metal nodes have great potential in the application of heterogeneous catalysis. However, identifying the real active site in MOF structures and tuning its amount to further improve its catalytic performance are still a great challenge. In this paper, defective UiO-66 modulated with trifluoroacetic acid (TFA) was synthesized and used for the conversion of cyclohexanone to cyclohexanol via hydrogen transfer. We found that not all structural defects were responsible for catalytic reaction, and only structural defects where open metal sites are created by a modulator were effective for cyclohexanone conversion. Then we successfully tuned the number of each type of effective structural defect (that is, missing-cluster defects or missing-linker defects) in modulated UiO-66 via precise control of the synthetic/treatment conditions. Our experimental results showed that the creation of both types of structural defects can increase the amount of effective open metal sites and then enhance their catalytic performances under the same conditions. Furthermore, the mechanism study confirmed that this reaction indeed proceeded on effective open metal sites. Our findings have further deepened the understanding of the roles of structural defects in MOF heterogeneous catalysis.

AB - Metal-organic frameworks (MOFs) with a high density of metal nodes have great potential in the application of heterogeneous catalysis. However, identifying the real active site in MOF structures and tuning its amount to further improve its catalytic performance are still a great challenge. In this paper, defective UiO-66 modulated with trifluoroacetic acid (TFA) was synthesized and used for the conversion of cyclohexanone to cyclohexanol via hydrogen transfer. We found that not all structural defects were responsible for catalytic reaction, and only structural defects where open metal sites are created by a modulator were effective for cyclohexanone conversion. Then we successfully tuned the number of each type of effective structural defect (that is, missing-cluster defects or missing-linker defects) in modulated UiO-66 via precise control of the synthetic/treatment conditions. Our experimental results showed that the creation of both types of structural defects can increase the amount of effective open metal sites and then enhance their catalytic performances under the same conditions. Furthermore, the mechanism study confirmed that this reaction indeed proceeded on effective open metal sites. Our findings have further deepened the understanding of the roles of structural defects in MOF heterogeneous catalysis.

UR - http://hdl.handle.net/10754/662155

UR - http://xlink.rsc.org/?DOI=C9TA12230C

UR - http://www.scopus.com/inward/record.url?scp=85080878426&partnerID=8YFLogxK

U2 - 10.1039/c9ta12230c

DO - 10.1039/c9ta12230c

M3 - Article

SN - 2050-7488

VL - 8

SP - 4464

EP - 4472

JO - Journal of Materials Chemistry A

JF - Journal of Materials Chemistry A

IS - 8

ER -

Engineering effective structural defects of metal-organic frameworks to enhance their catalytic performances

Abstract

Bibliographical note

Access to Document

Other files and links

Fingerprint

Cite this