Rational synthesis of porous materials and probing reactions in action within multipurpose in-situ cells

A joint Swedish-German collaboration within the Röntgen-Ångström Cluster (RÅC) supported by the Swedish Research Council and the Federal Ministry of Education and Research (BMBF), Germany.

The aim of the project is to investigate the formation of various types of porous materials and their interactions with guest molecules under reaction conditions by diffraction and spectroscopy techniques using synchrotron sources taking advantages of the high brilliance and tunable energy.

We design versatile, multi-purpose reaction cells for time resolved studies at variable temperatures and pressures. The reaction cells are developed in collaboration with the scientists in charge of the diffraction and spectroscopy beamlines at Petra III and MAX IV laboratory. The reaction cells are used at beamlines with different techniques, such as wide angle X-ray scattering (WAXS), small angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). They will be implemented at Petra III and MAX IV laboratory available to other users and different materials systems. The reaction cells are mainly designed for studies in liquids which are very challenging, but can also be used for gases. We combine the different synchrotron techniques to determine the average structures and local ordering (pair-distribution function, PDF) by total scattering and X-ray absorption spectroscopy (XAS).

We expect new and improved understanding of the formation of these materials and their interaction with the guest molecules. This knowledge is essential to rationally design new porous materials for different applications ranging from catalysis and gas separation to drug delivery.

SynRAC (synchrotron-based reaction cell for the analysis of chemical reactions)

N. Heidenreich, U. Rütt, M. Köppen, A. Ken Inge, S. Beier, A.-C. Dippel, R. Suren, and N. Stock
"A multi-purpose reaction cell for the investigation of reactions under solvothermal conditions"
Review of Scientific Instruments 2017, 88, 104102. DOI: 10.1063/1.4999688


J. Liang, J. Su, F. Peng, Y. Zeng, J. Sun
"PKU-21: A Novel Layered Germanate Built from Ge7 and Ge10 Clusters for CO2 Separation"
Chemistry - A European Journal 2017, accepted. DOI: 10.1002/chem.201704573


H. Reinsch, N. Stock
"Synthesis of MOFs: a Personal View on Rationalisation, Application and Exploration"
Dalton Transactions 2017, 46, 8339. DOI: 10.1039/C7DT01115F

T. Rhauderwiek, N. Heidenreich, H. Reinsch, S. Oeien-Oedegaard, K. A. Lomachenko, U. Ruett, A. V. Soldatov, K. P. Lillerud, N. Stock
"Co-Ligand Dependent Formation and Phase Transformation of Four Porphyrin-Based Cerium Metal-Organic Frameworks"
Crystal Growth & Design 2017, 17, 3462. DOI: 10.1021/acs.cgd.7b00450

M. Krueger, A. K. Inge, H. Reinsch, Y.-H. Li, M. Wahiduzzaman, C.-H. Lin, S.-L. Wang, G. Maurin, N. Stock
"Polymorphous Al-MOFs Based on V-Shaped Linker Molecules: Synthesis, Properties, and in Situ Investigation of Their Crystallization"
Inorganic Chemistry 2017, 56, 5851. DOI: 10.1021/acs.inorgchem.7b00202

B. Bueken, H. Reinsch, N. Heidenreich, A. Vandekerkhove, F. Vermoortele, C. E. A. Kirschhock, N. Stock, D. De Vos, R. Ameloot
"An In Situ Investigation of the Water-Induced Phase Transformation of UTSA-74 to MOF-74(Zn)"
CrystEngComm 2017, 19, 4152-4156. DOI: 10.1039/C7CE00094D

H. Reinsch, J. Benecke, M. Etter, N. Heidenreich, N. Stock
"Combined In- and Ex Situ Studies of Pyrazine Adsorption Into the Aliphatic MOF Al-CAU-13: Structures, Dynamics and Correlations"
Dalton Transactions 2017, 46, 1397. DOI: 10.1039/C6DT03998G

L. Ruiz Arana, P. Lindenberg, H. Said, M. Radke, N. Heidenreich, C. S. Cunha, S. Leubner, H. Terraschke
"Monitoring the Mechanism of Formation of [Ce(1,10-phenanthroline)2(NO3)3] by In-situ Luminescence Analysis of 5d-4f Electronic Transitions"
RSC Advances 2017, 7, 52794-52800. DOI: 10.1039/C7RA07488C

H. Terraschke, M. Rothe, P. Lindenberg
"In-Situ Monitoring Metal-Ligand Exchange Processes by Optical Spectroscopy and X-Ray Diffraction Analysis: A Review"
Reviews in Analytical Chemistry 2017. DOI: 10.1515/revac-2017-0003

H. Terraschke, M. Rothe, A.-M. Tsirigoni, P. Lindenberg, L. Ruiz Arana, N. Heidenreich, F. Bertram, M. Etter
"In-situ Luminescence Analysis: A New Light on Monitoring Calcium Phosphate Phase Transitions"
Inorganic Chemistry Frontiers 2017, 4, 1157. DOI: 10.1039/C7QI00172J

S. Springer, N. Heidenreich, N. Stock, L. van Wuellen, K. Huber, S. Leoni, M. Wiebcke
"The ZIF System Zinc(II) 4,5-Dichoroimidazolate: Theoretical and Experimental Investigations of the Polymorphism and Crystallization Mechanisms"
Zeitschrift für Kristallographie - Crystalline Materials 2017, 232, 77-90. DOI: 10.1515/zkri-2016-1968

Y. Wang, S. Takki, O. Cheung, H. Xu, W. Wan, L. R. Öhrström, A. K. Inge
"Elucidation of the Elusive Structure and Formula of the Active Pharmaceutical Ingredient Bismuth Subgallate By Continuous Rotation Electron Diffraction"
Journal 2017, 53, 7018. DOI: 10.1039/c7cc03180g

G. González Miera, A. Bermejo Gómez, P. J. Chupas, B. Martín-Matute, K. W. Chapman, A. E. Platero-Prats
"Topological Transformation of a Metal–Organic Framework Triggered by Ligand Exchange"
Inorganic Chemistry 2017, 56, 4576-4583. DOI: 10.1021/acs.inorgchem.7b00149

S. Roy, V. Pascanu, S. Pullen, G. González Miera, B. Martín-Matute, S. Ott
"Catalyst accessibility to chemical reductants in metal-organic frameworks"
Chemical Communications 2017, 53, 3257-3260. DOI: 10.1039/C7CC00022G

A. S. Etman, A. K. Inge, X. Jiaru, R. Younesi, K. Edström, J. Sun
"A Water Based Synthesis of Ultrathin Hydrated Vanadium Pentoxide Nanosheets for Lithium Battery Application: Free Standing Electrodes or Conventionally Casted Electrodes?"
Electrochimica Acta 2017, 252, 254-260. DOI: 10.1016/j.electacta.2017.08.137

Y. Luo, S. Smeets, F. Peng, A. S. Etman, Z. Wang, J. Sun, W. Yang
"Synthesis and Structure Determination of Large-Pore Zeolite SCM-14"
Chemistry - A European Journal 2017, 66, 16829-16834. DOI: 10.1002/chem.201703361

X.-L. Lv, K. Wang, B. Wang, J. Su, X. Zou, Y. Xue, J.-R. Li, H.-C. Zhou
"A Base-Resistant Metalloporphyrin Metal-Organic Framework for C-H Bond Halogenation"
Journal of the American Chemical Society 2017, 139, 211-217. DOI: 10.1021/jacs.6b09463

T. Willhammar, J. Su, Y. Yun, X. Zou, M. Afeworki, S. Weston, H. Vroman, W. W. Lonergan, K. G. Strohmaier
"High-Throughput Synthesis and Structure of Zeolite ZSM-43 with Two-Directional 8-Ring Channels"
Inorganic Chemistry 2017, 56, 8856-8864. DOI: 10.1021/acs.inorgchem.7b00752

A. Bruneau, K. P. J. Gustafson, N. Yuan, I. Persson, X. Zou, J.-E. Bäckvall
"Synthesis of Benzofurans and Indoles from Terminal Alkynes and Iodoaromatics Catalyzed by Recyclable Palladium Nanoparticles Immobilized on Siliceous Mesocellular Foam"
Chemistry - A European Journal 2017, 52, 12886-12891. DOI: 10.1002/chem.201702614

S. Smeets, Z. J. Berkson, D. Xie, S. I. Zones, W. Wan, X. Zou, M.-F. Hsieh, B. F. Chmelka, L. B. McCusker, C. Baerlocher
"Well-Defined Silanols in the Structure of the Calcined High-Silica Zeolite SSZ-70: New Understanding of a Successful Catalytic Material"
Journal of the American Chemical Society 2017, 139, 16803-16812. DOI: 10.1021/jacs.7b08810


M. Wendt, L. K. Mahnke, N. Heidenreich, W. Bensch
"Nucleation and Crystal Growth of a {V14Sb8O42} Cluster from a {V15Sb6O42} Polyoxovanadate: In Situ XRD Studies"
European Journal of Inorganic Chemistry 2016, 34, 5393-5398. DOI: 10.1002/ejic.201601025

N. Pienack, H. Terraschke, W. Bensch
"In-situ Crystallization Cell: Developments and First Results of the Model System Al(acac)3"
Zeitschrift für anorganische und allgemeine Chemie 2016, 642, 1040. DOI: 10.1002/zaac.20160504

M. C. Schlegel, D. Toebbens, R. Svetogorov, M. Krueger, N. Stock, H. Reinsch, D. Wallacher, R. Stewart, M. Russina
"Conformation-Controlled Hydrogen Storage in the CAU-1 Metal-Organic Framework"
Physical Chemistry Chemical Physics 2016, 18, 29258. DOI: 10.1039/C6CP05310F

A. S. Munn, R. S. Pillai, S. Biswas, N. Stock, G. Maurin, R. I. Walton
"The Flexibility of Modified Linker MIL-53 Materials"
Dalton Transactions 2016, 45, 4162. DOI: 10.1039/C5DT03438H

N. Pienack, L. Ruiz Arana, W. Bensch, H. Terraschke
"In-situ studies on phase transitions of Tris(acetylacetonato)-aluminum(III) Al(acac)3"
Crystals 2016, 6, 157. DOI: 10.3390/cryst6120157

A.-M. Tsirigoni, L. Ruiz Arana, P. Lindenberg, H. Terraschke
"In-situ Monitoring of Calcium Phosphate Phase Transitions: a Spectroscopic Approach"
Zeitschrift für anorganische und allgemeine Chemie 2016, 642, 1073. DOI: 10.1002/zaac.201605095

P. Polzin, I. V. Eliani, H. Terraschke
"Characterizing the Crystallization Kinetics of Ln(2,2’- Bipyridine)2(NO3)3 (Ln = Eu, Tb) by New in-situ Luminescence Analysis Technique"
Zeitschrift für anorganische und allgemeine Chemie 2016, 642, 1073. DOI: 10.1002/zaac.201605096

P. Lindenberg, L. Ruiz Arana, N. Heidenreich, H. Terraschke
"Polymorphism and In-Situ Detection of Reaction Intermediates on Eu(1,10-Phenanthroline)2(NO3)3"
Zeitschrift für anorganische und allgemeine Chemie 2016, 642, 1074. DOI: 10.1002/zaac.201605097

H. Terraschke, L. Ruiz Arana, P. Lindenberg, W. Bensch
"Development of a New In-Situ Analysis Technique Applying Luminescence of Local Coordination Sensors: Principle and Application for Monitoring Metal-Ligand Exchange Processes"
Analyst 2016, 141, 2588. DOI: 10.1039/C6AN00075D

A. K. Inge, T. Willhammar, K. E. Christensen, X. Zou
"A Germanate With a Collapsible Open-Framework"
Crystal Growth and Design 2016, 16, 6967. DOI: 10.1021/acs.cgd.6b01150

A. K. Inge, M. Köppen, J. Su, M. Feyand, H. Xu, X. Zou, M. O’Keeffe, N. Stock
"Unprecedented Topological Complexity in a Metal-Organic Framework Constructed from Simple Building Units"
Journal of the American Chemical Society 2016, 138, 1970. DOI: 10.1021/jacs.5b12484

V. Pascanu, F. Carson, M. Vico Solano, J. Su, X. Zou, M. J. Johansson, B. Martín-Matute
"Selective Heterogeneous C−H Activation/Halogenation Reactions Catalyzed by Pd@MOF Nanocomposites"
Chemistry - A European Journal 2016, 22, 3729. DOI: 10.1002/chem.201502918

E. Erbing, A. Vázquez-Romero, A. Bermejo Gómez, A. E. Platero-Prats, F. Carson, X. Zou, P. Tolstoy, B. Martín-Matute
"General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand"
Chemistry - A European Journal 2016, 44, 15659-15663. DOI: 10.1002/chem.201603825

O. Cheung, D. Wardecki, Z. Bacsik, P. Vasiliev, L. B. McCusker, N. Hedin
"Highly selective uptake of carbon dioxide on the zeolite |Na10.2KCs0.8|-LTA – a possible sorbent for biogas upgrading"
Physical Chemistry Chemical Physics 2016, 18, 16080-16083. DOI: 10.1039/C6CP02443B

A. S. Etman, H. D. Asfaw, N. Yuan, J. Li, Z. Zhou, F. Peng, I. Persson, X. Zou, T. Gustafsson, K. Edström, J. Sun
"A one-step water based strategy for synthesizing hydrated vanadium pentoxide nanosheets from VO2(B) as free-standing electrodes for lithium battery applications"
Journal of Materials Chemistry A 2016, 4, 17988-18001. DOI: 10.1039/C6TA06571F

J. Shin, H. Xu, S. Seo, P. Guo, J. G. Min, J. Cho, P. A. Wight, X. Zou, S. B. Hong
"Targeted Synthesis of Two Super-Complex Zeolites with Embedded Isoreticular Structures"
Angewandte Chemie 2016, 16, 5012-5016. DOI: 10.1002/ange.201510726

I. A. Ibarra, A. Mace, S. Yang, J. Sun, S. Lee, J.-S. Chang, A. Laaksonen, M. Schröder, X. Zou
"Adsorption Properties of MFM-400 and MFM-401 with CO2 and Hydrocarbons: Selectivity Derived from Directed Supramolecular Interactions"
Inorganic Chemistry 2016, 55, 7219-7228. DOI: 10.1021/acs.inorgchem.6b00035

P. Guo, K. Strohmaier, H. Vroman, M. Afeworki, P. I. Ravikovitch, C. S. Paur, J. Sun, A. Burton, X. Zou
"Accurate structure determination of a borosilicate zeolite EMM-26 with two-dimensional 10 × 10 ring channels using rotation electron diffraction"
Inorganic Chemistry Frontiers 2016, 3, 1444-1448. DOI: 10.1039/C6QI00262E

B. Marler, M. Müller, H. Gies
"Structure and properties of ITQ-8: a hydrous layer silicate with microporous silicate layers"
Dalton Transactions 2016, 45, 10155-10164. DOI: 10.1039/C6DT00713A

Y. Chen, J. Su, S. Huang, J. Liang, X. Lin, F. Liao, J. Sun, Y. Wang, J. Lin, H. Gies
"PKU-20: A new silicogermanate constructed from sti and asv layers"
Microporous and Mesoporous Materials 2016, 224, 384-391. DOI: 10.1016/j.micromeso.2015.12.052


A. E. Platero-Prats, A. Bermejo Gómez, K. W. Chapman, B. Martín-Matute, X.Zou
"Functionalising metal–organic frameworks with metal complexes: the role of structural dynamics"
CrystEngComm 2015, 17, 7632. DOI: 10.1039/C5CE01732G

Q. Yao, A. Bermejo Gómez, J. Su, V. Pascanu, Y. Yun, H. Zheng, H. Chen, L. Liu, H. Abdelhamid, B. Martin-Matute, X. Zou
"A Series of Highly Stable Isoreticular Lanthanide Metal-Organic Frameworks with Expanding Pore Size and Tunable Luminescent Properties"
Chemistry of Materials 2015, 27, 5332. DOI: 10.1021/acs.chemmater.5b01711

F. Carson, E. Martínez-Castro, R. Marcos, G. González Miera, K. Jansson, X. Zou, B. Martín-Matute
"Effect of the functionalisation route on a Zr–MOF with an Ir–NHC complex"
Chemical Communications 2015, 51, 10864. DOI: 10.1039/C5CC03934G

F. Carson, V. Pascanu, A. Bermejo Gómez, Y. Zhang, A. E. Platero-Prats, X. Zou, B. Martín-Matute
"Influence of the Base on Pd@MIL-101–NH2(Cr) as a Catalyst for the Suzuki–Miyaura Cross-Coupling Reaction"
Chemistry - A European Journal 2015, 21, 10896. DOI: 10.1002/chem.201500843

V. Pascanu, A. Bermejo Gómez, C. Ayats, A. Platero-Prats, F. Carson, J. Su, Q. Yao, M. Pericàs, X. Zou, B. Martín-Matute
"A Double-Supported Silica – Metal-Organic Framework Palladium Nanocatalyst for Aerobic Oxidation of Alcohols under Batch and Continuous Flow Regimes"
ACS Catalysis 2015, 5, 472. DOI: 10.1021/cs501573c

V. Pascanu, P. R. Hansen, A. Bermejo Gómez, C. Ayats, A. E. Platero-Prats, M. J. Johansson, M. À. Pericàs, B. Martín-Matute
"Synthesis of highly functionalised biaryls via Suzuki-Miyaura cross-coupling catalysed by Pd@MOF under batch and continuous flow regimes"
ChemSusChem 2015, 8, 123. DOI: 10.1002/cssc.201402858

A. E. Platero-Prats, A. Bermejo Gómez, L. Samain, X. Zou, B. Martín-Matute
"The first one-pot synthesis of metal−organic frameworks multifunctionalised with two transition metal complexes"
Chemistry - A European Journal 2015, 21, 861. DOI: 10.1002/chem.201403909

H. Chen, J. Ju, Q. Meng, J. Su, C. Lin, Z. Zhou, G. Li, W. Wang, W. Gao, C. Zeng, C. Tang, J. Lin, T. Yang, J. Sun
"PKU-3: An HCl-Inclusive Aluminoborate for Strecker Reaction Solved by Combining RED and PXRD"
Journal of the American Chemical Society 2015, 137, 7047-7050. DOI: 10.1021/jacs.5b03685

J. Liang, J. Su, X. Luo, Y. Wang, H. Zheng, H. Chen, X. Zou, J. Lin, J. Sun
"A Crystalline Mesoporous Germanate with 48-Ring Channels for CO2 Separation"
Angewandte Chemie 2015, 25, 7398-7402. DOI: 10.1002/ange.201501718

S. A. Basnayake, J. Su, X. Zou, K. J. Balkus
"Carbonate-Based Zeolitic Imidazolate Framework for Highly Selective CO2 Capture"
Inorganic Chemistry 2015, 54, 1816-1821. DOI: 10.1021/ic5027174

Y. Yun, M. Hernández, W. Wan, X. Zou, J. L. Jordá, A. Cantín, F. Rey, A. Corma
"The first zeolite with a tri-directional extra-large 14-ring pore system derived using a phosphonium-based organic molecule"
Chemical Communications 2015, 51, 7602-7605. DOI: 10.1039/C4CC10317C

P. Guo, J. Shin, A. Greenaway, J. G. Min, J. Su, H. J. Choi, L. Liu, P. A. Cox, S. B. Hong, P. A. Wright, X. Zou
"A zeolite family with expanding structural complexity and embedded isoreticular structures"
Nature 2015, 524, 74-78. DOI: 10.1038/nature14575

Q. Zhang, J. Su, D. Feng, Z. Wei, X. Zou, H.-C. Zhou
"Piezofluorochromic Metal–Organic Framework: A Microscissor Lift"
Journal of the American Chemical Society 2015, 137, 10064-10067. DOI: 10.1021/jacs.5b04695


J. Liang, J. Su, Y. Wang, Y. Chen, X. Zou, F. Liao, J. Lin, J. Sun
"A 3D 12-Ring Zeolite with Ordered 4-Ring Vacancies Occupied by (H2O)2 Dimers"
Chemistry - A European Journal 2014, 49, 16097-16101. DOI: 10.1002/chem.201405449

H. Chen, Y. Zhang, Z.-B. Yu, J. Sun
"Layered V-B-O polyoxometalate nets linked by diethylenetriamine complexes with dangling amine groups"
Dalton Transactions 2014, 43, 15283-15286. DOI: 10.1039/C4DT01533A

R. Martínez-Franco, J. Sun, G. Sastre, Y. Yun, X. Zou, M. Moliner, A. Corma
"Supra-molecular assembly of aromatic proton sponges to direct the crystallization of extra-large-pore zeotypes"
Proceedings of the Royal Society A 2014, 470, 2166. DOI: 10.1098/rspa.2014.0107

P. Guo, L. Liu, Y. Yun, J. Su, H. Gies, H. Zhang, F.-S. Xiao, X. Zou
"Ab initio structure determination of interlayer expanded zeolites by single crystal rotation electron diffraction"
Dalton Transactions 2014, 43, 10593-10601. DOI: 10.1039/C4DT00458B

O. Cheung, J. Su, Z. Bacsik, J. Li, L. Samain, X. Zou, N. Hedin
"CO2 selective NaMg-CTS-1 and its structural formation from the titanium silicate based molecule sieve NaMg-ETS-4"
Microporous and Mesoporous Materials 2014, 198, 63-73. DOI: 10.1016/j.micromeso.2014.07.017

L. Fang, L. Liu, Y. Yun, A. K. Inge, W. Wan, X. Zou, F. Gao
"SU-77: An Open-Framework Germanate Containing 12 × 10 × 10-Ring Channels Solved by Combining Rotation Electron Diffraction and Powder X-ray Diffraction"
Crystal Growth and Design 2014, 14, 5072-5078. DOI: 10.1021/cg500681k

K. Wang, D. Feng, T.-F. Liu, J. Su, S. Yuan, Y.-P. Chen, M. Bosch, X. Zou, H.-C. Zhou
"A Series of Highly Stable Mesoporous Metalloporphyrin Fe-MOFs"
Journal of the American Chemical Society 2014, 136, 13983-13986. DOI: 10.1021/ja507269n