Cerium Metal–Organic Framework for Photocatalysis
Abstract
Ligand-to-metal charge transfer (LMCT) can bring about the separation of photogenerated charges. Here we calculate the electronic structures of metal–organic frameworks (MOFs) having the UiO-66 architecture and M6O4(OH)4 inorganometallic nodes with M = Zr, Hf, Th, Ti, U, or Ce. We find that LMCT is favorable only in the Ce case, where it is promoted by the low-lying empty 4f orbitals of Ce4+. We therefore propose that incorporating Ce4+ into the node is an effective way to facilitate LMCT in a MOF. In addition, we show that by functionalizing the linker, it should be possible to engineer the electronic structure of the Ce-MOF for a desired reaction (e.g., water splitting) while preserving favorable LMCT. Furthermore, we also find that linker functionalization with electron donating or withdrawing groups allows tuning of the LMCT energy, and increasing the number of functional groups on each linker enhances the tuning; these findings are encouraging for applying Ce-MOFs for visible-response photocatalytic water splitting.
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- OSTI Identifier:
- 2311182
- Grant/Contract Number:
- SC0008688; FG02-17ER16362
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 25; 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; Energy; Functionalization; Ligand to metal charge transfer; Metal organic frameworks; Metals
Citation Formats
Wu, Xin-Ping, Gagliardi, Laura, and Truhlar, Donald G. Cerium Metal–Organic Framework for Photocatalysis. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b03613.
Wu, Xin-Ping, Gagliardi, Laura, & Truhlar, Donald G. Cerium Metal–Organic Framework for Photocatalysis. United States. https://doi.org/10.1021/jacs.8b03613
Wu, Xin-Ping, Gagliardi, Laura, and Truhlar, Donald G. Mon .
"Cerium Metal–Organic Framework for Photocatalysis". United States. https://doi.org/10.1021/jacs.8b03613. https://www.osti.gov/servlets/purl/2311182.
@article{osti_2311182,
title = {Cerium Metal–Organic Framework for Photocatalysis},
author = {Wu, Xin-Ping and Gagliardi, Laura and Truhlar, Donald G.},
abstractNote = {Ligand-to-metal charge transfer (LMCT) can bring about the separation of photogenerated charges. Here we calculate the electronic structures of metal–organic frameworks (MOFs) having the UiO-66 architecture and M6O4(OH)4 inorganometallic nodes with M = Zr, Hf, Th, Ti, U, or Ce. We find that LMCT is favorable only in the Ce case, where it is promoted by the low-lying empty 4f orbitals of Ce4+. We therefore propose that incorporating Ce4+ into the node is an effective way to facilitate LMCT in a MOF. In addition, we show that by functionalizing the linker, it should be possible to engineer the electronic structure of the Ce-MOF for a desired reaction (e.g., water splitting) while preserving favorable LMCT. Furthermore, we also find that linker functionalization with electron donating or withdrawing groups allows tuning of the LMCT energy, and increasing the number of functional groups on each linker enhances the tuning; these findings are encouraging for applying Ce-MOFs for visible-response photocatalytic water splitting.},
doi = {10.1021/jacs.8b03613},
journal = {Journal of the American Chemical Society},
number = 25,
volume = 140,
place = {United States},
year = {Mon May 28 00:00:00 EDT 2018},
month = {Mon May 28 00:00:00 EDT 2018}
}
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Works referenced in this record:
Metal-Organic Frameworks: Opportunities for Catalysis
journal, September 2009
- Farrusseng, David; Aguado, Sonia; Pinel, Catherine
- Angewandte Chemie International Edition, Vol. 48, Issue 41
Emerging Multifunctional Metal-Organic Framework Materials
journal, July 2016
- Li, Bin; Wen, Hui-Min; Cui, Yuanjing
- Advanced Materials, Vol. 28, Issue 40
Metal–Organic Frameworks for Heterogeneous Basic Catalysis
journal, May 2017
- Zhu, Li; Liu, Xiao-Qin; Jiang, Hai-Long
- Chemical Reviews, Vol. 117, Issue 12
Computational Design of Functionalized Metal–Organic Framework Nodes for Catalysis
journal, December 2017
- Bernales, Varinia; Ortuño, Manuel A.; Truhlar, Donald G.
- ACS Central Science, Vol. 4, Issue 1
The current status of hydrogen storage in metal–organic frameworks—updated
journal, January 2011
- Sculley, Julian; Yuan, Daqiang; Zhou, Hong-Cai
- Energy & Environmental Science, Vol. 4, Issue 8
Hydrogen Storage in Metal–Organic Frameworks
journal, September 2011
- Suh, Myunghyun Paik; Park, Hye Jeong; Prasad, Thazhe Kootteri
- Chemical Reviews, Vol. 112, Issue 2, p. 782-835
Methane storage in metal–organic frameworks
journal, January 2014
- He, Yabing; Zhou, Wei; Qian, Guodong
- Chem. Soc. Rev., Vol. 43, Issue 16
Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites
journal, November 2009
- Britt, D.; Furukawa, H.; Wang, B.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 49, p. 20637-20640
Metal–Organic Frameworks for Separations
journal, September 2011
- Li, Jian-Rong; Sculley, Julian; Zhou, Hong-Cai
- Chemical Reviews, Vol. 112, Issue 2, p. 869-932
Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
journal, March 2012
- Bloch, E. D.; Queen, W. L.; Krishna, R.
- Science, Vol. 335, Issue 6076, p. 1606-1610
Photoreactivity examined through incorporation in metal−organic frameworks
journal, May 2010
- Blake, Alexander J.; Champness, Neil R.; Easun, Timothy L.
- Nature Chemistry, Vol. 2, Issue 8
Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic Photocatalysis
journal, August 2011
- Wang, Cheng; Xie, Zhigang; deKrafft, Kathryn E.
- Journal of the American Chemical Society, Vol. 133, Issue 34, p. 13445-13454
Studies on Photocatalytic CO 2 Reduction over NH 2 -Uio-66(Zr) and Its Derivatives: Towards a Better Understanding of Photocatalysis on Metal-Organic Frameworks
journal, September 2013
- Sun, Dengrong; Fu, Yanghe; Liu, Wenjun
- Chemistry - A European Journal, Vol. 19, Issue 42
Metal–organic frameworks for artificial photosynthesis and photocatalysis
journal, January 2014
- Zhang, Teng; Lin, Wenbin
- Chem. Soc. Rev., Vol. 43, Issue 16
Visible-Light Photoreduction of CO 2 in a Metal–Organic Framework: Boosting Electron–Hole Separation via Electron Trap States
journal, October 2015
- Xu, Hai-Qun; Hu, Jiahua; Wang, Dengke
- Journal of the American Chemical Society, Vol. 137, Issue 42
A panchromatic modification of the light absorption spectra of metal–organic frameworks
journal, January 2016
- Otal, E. H.; Kim, M. L.; Calvo, M. E.
- Chemical Communications, Vol. 52, Issue 40
A Titanium–Organic Framework: Engineering of the Band-Gap Energy for Photocatalytic Property Enhancement
journal, December 2016
- Nguyen, Ha L.; Vu, Thanh T.; Le, Dinh
- ACS Catalysis, Vol. 7, Issue 1
Fabrication of Ce doped UiO-66/graphene nanocomposites with enhanced visible light driven photoactivity for reduction of nitroaromatic compounds
journal, October 2017
- Yang, Zhiwang; Xu, Xueqing; Liang, Xixi
- Applied Surface Science, Vol. 420
Plasmon-Enhanced Photocatalytic CO 2 Conversion within Metal–Organic Frameworks under Visible Light
journal, December 2016
- Choi, Kyung Min; Kim, Dohyung; Rungtaweevoranit, Bunyarat
- Journal of the American Chemical Society, Vol. 139, Issue 1
Band gap modulation of functionalized metal–organic frameworks
journal, January 2014
- Musho, Terence; Li, Jiangtan; Wu, Nianqiang
- Phys. Chem. Chem. Phys., Vol. 16, Issue 43
Computational exploration of newly synthesized zirconium metal–organic frameworks UiO-66, -67, -68 and analogues
journal, January 2014
- Yang, Li-Ming; Ganz, Eric; Svelle, Stian
- J. Mater. Chem. C, Vol. 2, Issue 34
Understanding Intrinsic Light Absorption Properties of UiO-66 Frameworks: A Combined Theoretical and Experimental Study
journal, November 2015
- Hendrickx, Kevin; Vanpoucke, Danny E. P.; Leus, Karen
- Inorganic Chemistry, Vol. 54, Issue 22
Modelling a Linker Mix-and-Match Approach for Controlling the Optical Excitation Gaps and Band Alignment of Zeolitic Imidazolate Frameworks
journal, November 2016
- Grau-Crespo, Ricardo; Aziz, Alex; Collins, Angus W.
- Angewandte Chemie International Edition, Vol. 55, Issue 52
Study of the inorganic substitution in a functionalized UiO-66 metal–organic framework
journal, January 2016
- Yasin, Alhassan Salman; Li, Jiangtian; Wu, Nianqiang
- Physical Chemistry Chemical Physics, Vol. 18, Issue 18
Electronic origins of photocatalytic activity in d0 metal organic frameworks
journal, March 2016
- Nasalevich, Maxim A.; Hendon, Christopher H.; Santaclara, Jara G.
- Scientific Reports, Vol. 6, Issue 1
Missing Linkers: An Alternative Pathway to UiO-66 Electronic Structure Engineering
journal, March 2017
- De Vos, Arthur; Hendrickx, Kevin; Van Der Voort, Pascal
- Chemistry of Materials, Vol. 29, Issue 7
Revisiting the Incorporation of Ti(IV) in UiO-type Metal–Organic Frameworks: Metal Exchange versus Grafting and Their Implications on Photocatalysis
journal, October 2017
- Santaclara, Jara G.; Olivos-Suarez, Alma I.; Gonzalez-Nelson, Adrian
- Chemistry of Materials, Vol. 29, Issue 21
Understanding metal–organic frameworks for photocatalytic solar fuel production
journal, January 2017
- Santaclara, J. G.; Kapteijn, F.; Gascon, J.
- CrystEngComm, Vol. 19, Issue 29
[Ti 8 Zr 2 O 12 (COO) 16 ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks
journal, November 2017
- Yuan, Shuai; Qin, Jun-Sheng; Xu, Hai-Qun
- ACS Central Science, Vol. 4, Issue 1
Effects of ligand functionalization on the photocatalytic properties of titanium-based MOF: A density functional theory study
journal, March 2018
- Li, Yi; Fu, Yuqing; Ni, Bilian
- AIP Advances, Vol. 8, Issue 3
Metal-organic frameworks with high capacity and selectivity for harmful gases
journal, August 2008
- Britt, D.; Tranchemontagne, D.; Yaghi, O. M.
- Proceedings of the National Academy of Sciences, Vol. 105, Issue 33, p. 11623-11627
Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011
- Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
- Chemical Reviews, Vol. 112, Issue 2, p. 724-781
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008
- Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
- Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
De facto methodologies toward the synthesis and scale-up production of UiO-66-type metal–organic frameworks and membrane materials
journal, January 2015
- Hu, Zhigang; Zhao, Dan
- Dalton Transactions, Vol. 44, Issue 44
Postsynthetic Modification of Zirconium Metal-Organic Frameworks: Postsynthetic Modification of Zirconium Metal-Organic Frameworks
journal, July 2016
- Marshall, Ross J.; Forgan, Ross S.
- European Journal of Inorganic Chemistry, Vol. 2016, Issue 27
Structural determination of a highly stable metal-organic framework with possible application to interim radioactive waste scavenging: Hf-UiO-66
journal, September 2012
- Jakobsen, Søren; Gianolio, Diego; Wragg, David S.
- Physical Review B, Vol. 86, Issue 12
Three-Dimensional MOF-Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U 6 O 8 )
journal, January 2013
- Falaise, Clément; Volkringer, Christophe; Vigier, Jean-François
- Chemistry - A European Journal, Vol. 19, Issue 17
Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity
journal, January 2015
- Lammert, Martin; Wharmby, Michael T.; Smolders, Simon
- Chemical Communications, Vol. 51, Issue 63
Coordination polymers of uranium( iv ) terephthalates
journal, January 2015
- Falaise, Clément; Assen, Ayalew; Mihalcea, Ionut
- Dalton Transactions, Vol. 44, Issue 6
Thorium Terephthalates Coordination Polymers Synthesized in Solvothermal DMF/H 2 O System
journal, February 2015
- Falaise, Clément; Charles, Jean-Sébastien; Volkringer, Christophe
- Inorganic Chemistry, Vol. 54, Issue 5
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006
- Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
- The Journal of Chemical Physics, Vol. 125, Issue 22
Electronic Chemical Potentials of Porous Metal–Organic Frameworks
journal, February 2014
- Butler, Keith T.; Hendon, Christopher H.; Walsh, Aron
- Journal of the American Chemical Society, Vol. 136, Issue 7
Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold
journal, March 1998
- Casida, Mark E.; Jamorski, Christine; Casida, Kim C.
- The Journal of Chemical Physics, Vol. 108, Issue 11
Energy‐adjusted a b i n i t i o pseudopotentials for the rare earth elements
journal, February 1989
- Dolg, M.; Stoll, H.; Preuss, H.
- The Journal of Chemical Physics, Vol. 90, Issue 3
Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications
journal, June 2016
- Pattengale, Brian; Yang, Sizhuo; Ludwig, John
- Journal of the American Chemical Society, Vol. 138, Issue 26
Photochemistry of Zr-based MOFs: ligand-to-cluster charge transfer, energy transfer and excimer formation, what else is there?
journal, January 2016
- Gutierrez, Mario; Cohen, Boiko; Sánchez, Félix
- Physical Chemistry Chemical Physics, Vol. 18, Issue 40
Density functional theory studies of the structure and electronic structure of pure and defective low index surfaces of ceria
journal, February 2005
- Nolan, Michael; Grigoleit, Sonja; Sayle, Dean C.
- Surface Science, Vol. 576, Issue 1-3
Modeling of , , and in the formalism
journal, January 2007
- Andersson, D. A.; Simak, S. I.; Johansson, B.
- Physical Review B, Vol. 75, Issue 3
B3LYP calculations of cerium oxides
journal, February 2010
- Kullgren, Jolla; Castleton, Christopher W. M.; Müller, Carsten
- The Journal of Chemical Physics, Vol. 132, Issue 5
Electron Localization Determines Defect Formation on Ceria Substrates
journal, July 2005
- Esch, F.
- Science, Vol. 309, Issue 5735
Electron Localization in Defective Ceria Films: A Study with Scanning-Tunneling Microscopy and Density-Functional Theory
journal, June 2011
- Jerratsch, Jan-Frederik; Shao, Xiang; Nilius, Niklas
- Physical Review Letters, Vol. 106, Issue 24
Clustering of Oxygen Vacancies at : Critical Role of Hydroxyls
journal, February 2016
- Wu, Xin-Ping; Gong, Xue-Qing
- Physical Review Letters, Vol. 116, Issue 8
Synthesis of Ce ions doped metal–organic framework for promoting catalytic H 2 production from ammonia borane under visible light irradiation
journal, January 2015
- Wen, Meicheng; Kuwahara, Yasutaka; Mori, Kohsuke
- Journal of Materials Chemistry A, Vol. 3, Issue 27
Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory
journal, April 2011
- Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin
- Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718
Solar Water Splitting Cells
journal, November 2010
- Walter, Michael G.; Warren, Emily L.; McKone, James R.
- Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances
journal, January 2014
- Wang, Huanli; Zhang, Lisha; Chen, Zhigang
- Chemical Society Reviews, Vol. 43, Issue 15
Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting
journal, January 2014
- Hisatomi, Takashi; Kubota, Jun; Domen, Kazunari
- Chem. Soc. Rev., Vol. 43, Issue 22
Band Gap Engineering of MnO via ZnO Alloying: A Potential New Visible-Light Photocatalyst
journal, April 2012
- Kanan, Dalal K.; Carter, Emily A.
- The Journal of Physical Chemistry C, Vol. 116, Issue 18, p. 9876-9887
Aqueous Solvation Free Energies of Ions and Ion−Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
journal, August 2006
- Kelly, Casey P.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 110, Issue 32
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents
journal, June 2010
- Isse, Abdirisak A.; Gennaro, Armando
- The Journal of Physical Chemistry B, Vol. 114, Issue 23
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels
journal, January 2014
- Qiao, Jinli; Liu, Yuyu; Hong, Feng
- Chem. Soc. Rev., Vol. 43, Issue 2
Ultraviolet and Infrared Absorption Spectra of Substituted Acetophenones and Benzoic Acids
journal, February 1956
- Tanaka, Jiro; Nagakura, Saburo; Kobayashi, Michio
- The Journal of Chemical Physics, Vol. 24, Issue 2
Iodine—acetophenone charge-transfer complexes
journal, January 1984
- Medina, R. M.; García-Vázquez, J. A.; Macazaga, M. J.
- Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 40, Issue 1
Exploring Lanthanide Doping in UiO-66: A Combined Experimental and Computational Study of the Electronic Structure
journal, April 2018
- Hendrickx, Kevin; Joos, Jonas J.; De Vos, Arthur
- Inorganic Chemistry, Vol. 57, Issue 9