Unni Olsbye

• Bai, Yunfei; Cordero-Lanzac, Tomás; Nova Flores, Ainara; Olsbye, Unni; Taarning, Esben & Martinez-Espin, Juan S. (2024). Selective linear ethylene oligomerization over nickel-containing zeotypes with tetravalent framework heteroatoms. Catalysis Science & Technology. ISSN 2044-4753. doi: 10.1039/d3cy01736b.
• Gerz, Isabelle; Aunan, Erlend ; Finelli, Valeria; Abu Rasheed, Mouhammad; Deplano, Gabriele & Cortez Sgroi Pupo, Rafael [Show all 15 contributors for this article] (2024). Enabling a bioinspired N,N,N-copper coordination motif through spatial control in UiO-67: synthesis and reactivity. Dalton Transactions. ISSN 1477-9226. doi: 10.1039/d3dt03096b.
• Skorynina, Alina A.; Lazzarini, Andrea; Sannes, Dag Kristian; Kozyr, Elizaveta G.; Ahoba-Sam, Christian & Bordiga, Silvia [Show all 8 contributors for this article] (2024). The structure of Pd-functionalized UiO-67 during CO<inf>2</inf> hydrogenation. Journal of Materials Chemistry C. ISSN 2050-7526. 10. doi: 10.1039/d3tc04175a.
• Jessy, Abou Nakad; Firth, Daniel Sean; Bisiriyu, Muhammad Taoheed; Szeto, Kai C.; Merle, Nicolas & De Mallmann, Aimery [Show all 10 contributors for this article] (2024). Ga(iBu)<inf>3</inf> supported on meso H-ZSM-5: Effect of Si/Al ratio on the activity and selectivity in propane aromatization. Catalysis communications. ISSN 1566-7367. 187. doi: 10.1016/j.catcom.2023.106825.
• Cordero Lanzac, Tomas; Capel Berdiell, Izar; Airi, Alessia; Chung, Sang-Ho; Mancuso, Jenna & Redekop, Evgeniy [Show all 16 contributors for this article] (2024). Transitioning from Methanol to Olefins (MTO) toward a Tandem CO<inf>2</inf> Hydrogenation Process: On the Role and Fate of Heteroatoms (Mg, Si) in MAPO-18 Zeotypes. JACS Au. ISSN 2691-3704. doi: 10.1021/jacsau.3c00768. Full text in Research Archive
• Pulumati, Sri Harsha; Sannes, Dag Kristian; Jabbour, Christia R.; Mandemaker, Laurens D. B.; Weckhuysen, Bert M. & Olsbye, Unni [Show all 8 contributors for this article] (2023). Mechanistic Insights in the Catalytic Hydrogenation of CO<inf>2</inf> over Pt Nanoparticles in UiO-67 Metal-Organic Frameworks. ACS Catalysis. ISSN 2155-5435. 14(1), p. 382–394. doi: 10.1021/acscatal.3c03401. Full text in Research Archive
• Redekop, Evgeniy; Cordero-Lanzac, Tomás; Salusso, Davide; Pokle, Anuj; Øien-Ødegaard, Sigurd & Sunding, Martin Fleissner [Show all 11 contributors for this article] (2023). Zn Redistribution and Volatility in ZnZrOx Catalysts for CO2 Hydrogenation. Chemistry of Materials. ISSN 0897-4756. 35(24), p. 10434–10445. doi: 10.1021/acs.chemmater.3c01632.
• Prodinger, Sebastian; Capel Berdiell, Izar; Cordero-Lanzac, Tomas; Bygdnes, Odd Reidar; Solemsli, Bjørn Gading & Kvande, Karoline [Show all 10 contributors for this article] (2023). Cation-induced speciation of port-size during mordenite zeolite synthesis. Journal of Materials Chemistry A. ISSN 2050-7488. 11(40), p. 21884–21894. doi: 10.1039/d3ta03444e. Full text in Research Archive Show summary

  Mordenite (MOR) zeolite, an important industrial catalyst exists in two, isostructural variants defined by their port-size, small and large-port. Here we show for the first time how a systematic, single-parameter variation influences the synthesis out-come on the final MOR material leading to distinctly different catalysts. The cation identity has a direct impact on the synthesis mechanism with potassium cations generating the more constrained, small-port MOR variant compared to the large-port obtained with sodium cations. This was expressed by different degrees of accessibility ascertained with a combination of toluene breakthrough and temperature programmed desorption (TPD), propylamine TPD, as well as sterically sensitive isobutane conversion. Rietveld refinement of the X-ray diffractograms elucidated the preferential siting of the smaller sodium cations in the constricted 8-ring, from which differences in Al distribution follow. Note, there are no organic structure directing agents utilized in this synthesis pointing at the important role of inorganic structure directing agents (ISDA).

• Tezel, Elif; Sannes, Dag Kristian; Svelle, Stian; Szilagyi, Petra Agota & Olsbye, Unni (2023). Direct CO<inf>2</inf> to methanol reduction on Zr<inf>6</inf>-MOF based composite catalysts: a critical review. Materials Advances. ISSN 2633-5409. doi: 10.1039/d3ma00345k. Show summary

  The pressing problem of climate change on account of anthropogenic greenhouse-gas emissions underlines the necessity for carbon capture and utilisation technologies. Several heterogeneous catalyst systems allowing the conversion of waste CO2 into desirable products, such as methanol, have emerged as promising and potentially viable solutions to this perennial problem. In particular, composite catalysts based on hexanuclear zirconium metal–organic framework matrices have shown much promise in the direct conversion of CO2 into value-added and useful products. Herein, we critically review the literature in this area and relate differences in composition, defect chemistry, and structural characteristics, their reaction conditions with their performance and stability in the thermocatalytic hydrogenation of CO2 to methanol, on the basis of both experimental and theoretical studies. We also highlight the obstacles in directly comparing the performance of these systems for CO2 hydrogenation and suggest potential solutions and opportunities for further advancement.

• Xie, Jingxiu & Olsbye, Unni (2023). The Oxygenate-Mediated Conversion of CO<inf>x</inf> to Hydrocarbons─On the Role of Zeolites in Tandem Catalysis. Chemical Reviews. ISSN 0009-2665. 123(20), p. 11775–11816. doi: 10.1021/acs.chemrev.3c00058. Show summary

  Decentralized chemical plants close to circular carbon sources will play an important role in shaping the postfossil society. This scenario calls for carbon technologies which valorize CO2 and CO with renewable H2 and utilize process intensification approaches. The single-reactor tandem reaction approach to convert COx to hydrocarbons via oxygenate intermediates offers clear benefits in terms of improved thermodynamics and energy efficiency. Simultaneously, challenges and complexity in terms of catalyst material and mechanism, reactor, and process gaps have to be addressed. While the separate processes, namely methanol synthesis and methanol to hydrocarbons, are commercialized and extensively discussed, this review focuses on the zeolite/zeotype function in the oxygenate-mediated conversion of COx to hydrocarbons. Use of shape-selective zeolite/zeotype catalysts enables the selective production of fuel components as well as key intermediates for the chemical industry, such as BTX, gasoline, light olefins, and C3+ alkanes. In contrast to the separate processes which use methanol as a platform, this review examines the potential of methanol, dimethyl ether, and ketene as possible oxygenate intermediates in separate chapters. We explore the connection between literature on the individual reactions for converting oxygenates and the tandem reaction, so as to identify transferable knowledge from the individual processes which could drive progress in the intensification of the tandem process. This encompasses a multiscale approach, from molecule (mechanism, oxygenate molecule), to catalyst, to reactor configuration, and finally to process level. Finally, we present our perspectives on related emerging technologies, outstanding challenges, and potential directions for future research.

• Kvande, Karoline; Garetto, Beatrice; Deplano, Gabriele; Signorile, Matteo; Solemsli, Bjørn Gading & Prodinger, Sebastian [Show all 11 contributors for this article] (2023). Understanding C-H activation in light alkanes over Cu-MOR zeolites by coupling advanced spectroscopy and temperature-programmed reduction experiments. Chemical Science. ISSN 2041-6520. doi: 10.1039/d3sc01677c. Full text in Research Archive
• Kvande, Karoline; Mawanga, Moses; Prodinger, Sebastian; Solemsli, Bjørn Gading; Yang, Jia & Olsbye, Unni [Show all 9 contributors for this article] (2023). Microcalorimetry on Cu-MCM-22 Reveals Structure-Activity Relationships for the Methane-to-Methanol Reaction. Industrial & Engineering Chemistry Research. ISSN 0888-5885. 62(28), p. 10939–10950. doi: 10.1021/acs.iecr.3c00988. Full text in Research Archive
• Kvande, Karoline; Prodinger, Sebastian; Solemsli, Bjørn Gading; Bordiga, Silvia; Borfecchia, Elisa & Olsbye, Unni [Show all 8 contributors for this article] (2023). Cu-loaded zeolites enable the selective activation of ethane to ethylene at low temperatures and pressure. Chemical Communications. ISSN 1359-7345. 40. doi: 10.1039/d3cc00948c. Full text in Research Archive
• Sannes, Dag Kristian; Øien-Ødegaard, Sigurd; Aunan, Erlend ; Nova, Ainara & Olsbye, Unni (2023). Quantification of Linker Defects in UiO-Type Metal-Organic Frameworks. Chemistry of Materials. ISSN 0897-4756. 35(10), p. 3793–3800. doi: 10.1021/acs.chemmater.2c03744. Full text in Research Archive
• Ticali, Pierfrancesco; Salusso, Davide; Airi, Alessia; Morandi, Sara; Borfecchia, Elisa & Ramirez, Adrian [Show all 11 contributors for this article] (2023). From Lab to Technical CO2 Hydrogenation Catalysts: Understanding PdZn Decomposition. ACS Applied Materials & Interfaces. ISSN 1944-8244. 15(4), p. 5218–5228. doi: 10.1021/acsami.2c19357. Full text in Research Archive
• Cordero-Lanzac, Tomas; Ramirez, Adrian; Cruz-Fernandez, Marta; Zander, Hans-Jörg; Joensen, Finn & Woolas, Steven [Show all 10 contributors for this article] (2023). A CO2 valorization plant to produce light hydrocarbons: Kinetic model, process design and life cycle assessment. Journal of CO2 Utilization. ISSN 2212-9820. 67. doi: 10.1016/j.jcou.2022.102337. Full text in Research Archive
• Wang, Sen; Zhang, Li; Wang, Pengfei; Jiao, Weiyong; Qin, Zhangfeng & Dong, Mei [Show all 9 contributors for this article] (2022). Highly selective hydrogenation of CO2 to propane over GaZrO x/H-SSZ-13 composite. Nature Catalysis. ISSN 2520-1158. 5(11), p. 1038–1050. doi: 10.1038/s41929-022-00871-7. Full text in Research Archive
• Kalantzopoulos, Georgios; Rojo Gama, Daniel; Pappas, Dimitrios; Dovgaliuk, Iurii; Olsbye, Unni & Beato, Pablo [Show all 9 contributors for this article] (2022). Real-time regeneration of a working zeolite monitored via operando X-ray diffraction and crystallographic imaging: how coke flees the MFI framework. Dalton Transactions. ISSN 1477-9226. 51(44), p. 16845–16851. doi: 10.1039/d2dt02845j. Full text in Research Archive
• Genz, Nina; Kallio, Antti-Jussi; Oord, Ramon; Krumeich, Frank; Pokle, Anuj & Prytz, Øystein [Show all 10 contributors for this article] (2022). Operando Laboratory-Based Multi-Edge X-Ray Absorption Near-Edge Spectroscopy of Solid Catalysts. Angewandte Chemie International Edition. ISSN 1433-7851. 61(48). doi: 10.1002/anie.202209334. Full text in Research Archive
• Redekop, Evgeniy; Poelman, Hilde; Filez, Matthias; Ramachandran, Ranjith K.; Dendooven, Jolien & Detavernier, Christophe [Show all 9 contributors for this article] (2022). Aligning time-resolved kinetics (TAP) and surface spectroscopy (AP-XPS) for a more comprehensive understanding of ALD-derived 2D and 3D model catalysts. Faraday discussions. ISSN 1359-6640. 236, p. 485–509. doi: 10.1039/d1fd00120e.
• Airi, Alessia; Damin, Alessandro; Xie, Jingxiu; Olsbye, Unni & Bordiga, Silvia (2022). Catalyst sites and active species in the early stages of MTO conversion over cobalt AlPO-18 followed by IR spectroscopy. Catalysis Science & Technology. ISSN 2044-4753. doi: 10.1039/d2cy00303a. Full text in Research Archive
• Shostak, Vladyslav; Redekop, Evgeniy & Olsbye, Unni (2022). Parametric sensitivity analysis of the transient adsorption-diffusion models for hydrocarbon transport in microporous materials. Catalysis Today. ISSN 0920-5861. doi: 10.1016/j.cattod.2022.05.050. Full text in Research Archive Show summary

  The complex nature of hydrocarbon transport in microporous materials offers unique challenges for the description of transient kinetic data in catalysis by e.g. acidic zeolites and zeotypes. Currently, very few models in the literature capture such phenomena as surface barriers or hindered microporous diffusion - processes that are known to impact gas transport during the kinetic studies of zeolite catalyzed reactions. In this work we provide extended models that reflect the aforementioned phenomena during pulse-response experiments in the Temporal Analysis of Products (TAP) reactor. Systematic studies of models’ parametric sensitivity are presented to assist the design of future experiments. Numerical simulations are used to investigate how thermodynamic adsorption properties of realistic zeolites can affect the pulse-response shapes. For certain combination adsorption/diffusion parameters, microporous diffusion is shown to result in a characteristic bend in the mean residence time temperature dependency, which can be used as a fingerprint in model discrimination.

• Wang, Sen; Zhang, Li; Wang, Pengfei; Liu, Xingchen; Chen, Yanyan & Qin, Zhangfeng [Show all 11 contributors for this article] (2022). Highly effective conversion of CO2 into light olefins abundant in ethene. Chem. ISSN 2451-9308. 8(5), p. 1376–1394. doi: 10.1016/j.chempr.2022.01.004. Full text in Research Archive
• Zhang, Lina; Firth, Daniel Sean; Olsbye, Unni & Bao, Xiaojun (2022). Two-Step Dry Gel Method Produces MgAPO-11 with Low Aspect Ratio and Improved Catalytic Performance in the Conversion of Methanol to Hydrocarbons. Catalysts. ISSN 2073-4344. 12(4), p. 1–11. doi: 10.3390/catal12040413. Full text in Research Archive
• Li, Lu; Chavan, Sachin Maruti; Ganjkhanlou, Yadolah; Groppo, Elena; Sagstuen, Einar & Bordiga, Silvia [Show all 8 contributors for this article] (2022). Characterization of the NiSO4 site on a NiSO4-ReOx/γ-Al2O3 catalyst for tandem conversion of ethylene to propylene. Applied Catalysis A : General. ISSN 0926-860X. 637. doi: 10.1016/j.apcata.2022.118598. Show summary

  A series of NiSO4-ReOx/Al2O3 catalysts were synthesized by a co-impregnation method, tested in the conversion of ethylene to propylene at mild conditions, and thoroughly characterized by different spectroscopy techniques. In particular, the attention was focused on the NiSO4 function, which is directly involved in ethylene conversion to 2-butylene, but also drives the catalyst deactivation. Results shows that the sulfate anions increase the surface acidity of alumina, and simultaneously influence the electronic properties of the Ni sites. Indeed, thermal activation of the catalyst promotes the formation of covalent bonds between the sulfate anions and the Ni2+ or Al3+ cations, while keeping constant the + 2 oxidation state of the Ni sites. Studying the initial steps of the ETP reaction reveals the primary acid-catalyzed formation of branched oligomers. Catalyst deactivation could be due to formation and adsorption of long-chain oligomers, or less interaction of sulfate anions with Ni ions.

• Xie, Jingxiu; Firth, Daniel Sean; Cordero Lanzac, Tomas; Airi, Alessia; Negri, Chiara & Øien-Ødegaard, Sigurd [Show all 9 contributors for this article] (2022). MAPO-18 Catalysts for the Methanol to Olefins Process: Influence of Catalyst Acidity in a High-Pressure Syngas (CO and H2) Environment. ACS Catalysis. ISSN 2155-5435. 12, p. 1520–1531. doi: 10.1021/acscatal.1c04694. Full text in Research Archive
• Ticali, Pierfrancesco; Salusso, Davide; Ahmad, Rafia; Ahoba-Sam, Christian; Ramirez, Adrian & Shterk, Genrikh [Show all 13 contributors for this article] (2021). CO2 hydrogenation to methanol and hydrocarbons over bifunctional Zn-doped ZrO2/zeolite catalysts. Catalysis Science & Technology. ISSN 2044-4753. 11(4), p. 1249–1268. doi: 10.1039/d0cy01550d.
• Narciso, Javier; Ramos-Fernandez, Enrique; Delgado-Marín, José; Affolter, Christopher; Olsbye, Unni & Redekop, Evgeniy (2021). New route for the synthesis of Co-MOF from metal substrates. Microporous and Mesoporous Materials. ISSN 1387-1811. 324. doi: 10.1016/j.micromeso.2021.111310.
• Ramirez, Adrian; Ticali, Pierfrancesco; Salusso, Davide; Cordero Lanzac, Tomas; Ould-Chikh, Samy & Ahoba-Sam, Christian [Show all 13 contributors for this article] (2021). Multifunctional Catalyst Combination for the Direct Conversion of CO<inf>2</inf>to Propane. JACS Au. ISSN 2691-3704. 1(10), p. 1719–1732. doi: 10.1021/jacsau.1c00302.
• Mortén, Magnus; Cordero Lanzac, Tomas; Cnudde, Pieter; Redekop, Evgeniy; Svelle, Stian & Van Speybroeck, Veronique [Show all 7 contributors for this article] (2021). Acidity effect on benzene methylation kinetics over substituted H-MeAlPO-5 catalysts. Journal of Catalysis. ISSN 0021-9517. 404, p. 594–606. doi: 10.1016/j.jcat.2021.11.002. Full text in Research Archive
• Gerz, Isabelle; Jannuzzi, Sergio Augusto Venturinelli; Hylland, Knut Tormodssønn; Negri, Chiara; Wragg, David Stephen & Øien-Ødegaard, Sigurd [Show all 10 contributors for this article] (2021). Structural Elucidation, Aggregation, and Dynamic Behaviour of N,N,N,N-Copper(I) Schiff Base Complexes in Solid and in Solution: A Combined NMR, X-ray Spectroscopic and Crystallographic Investigation. European Journal of Inorganic Chemistry (EurJIC). ISSN 1434-1948. doi: 10.1002/ejic.202100722. Full text in Research Archive
• Pinilla Herrero, Irene; Borfecchia, Elisa; Cordero-Lanzac, Tomás; Mentzel, Uffe V.; Joensen, Finn & Lomachenko, Kirill A. [Show all 10 contributors for this article] (2021). Finding the active species: The conversion of methanol to aromatics over Zn-ZSM-5/alumina shaped catalysts. Journal of Catalysis. ISSN 0021-9517. 394, p. 416–428. doi: 10.1016/j.jcat.2020.10.024.
• Redekop, Evgeniy; Johansson, Niclas; Kokkonen, Esko; Urpelainen, Samuli; Lopes Da Silva, Felipe & Kaipio, Mikko [Show all 11 contributors for this article] (2021). Synchronizing gas injections and time-resolved data acquisition for perturbation-enhanced APXPS experiments. Review of Scientific Instruments. ISSN 0034-6748. 92(4), p. 044101-1–044101-11. doi: 10.1063/5.0039957.
• Aunan, Erlend ; Affolter, Chris W.; Olsbye, Unni & Lillerud, Karl Petter (2021). Modulation of the Thermochemical Stability and Adsorptive Properties of MOF-808 by the Selection of Non-structural Ligands. Chemistry of Materials. ISSN 0897-4756. 33(4), p. 1471–1476. doi: 10.1021/acs.chemmater.0c04823. Full text in Research Archive
• Cnudde, Pieter; Redekop, Evgeniy; Dai, Weili; Porcaro, Natale G.; Waroquier, Michel & Bordiga, Silvia [Show all 10 contributors for this article] (2021). Experimental and theoretical evidence for promotional effect of acid sites on the diffusion of alkenes through small-pore zeolites. Angewandte Chemie International Edition. ISSN 1433-7851. doi: 10.1002/anie.202017025. Full text in Research Archive
• Wang, Sen; Zhang, Li; Zhang, Wenyu; Wang, Pengfei; Qin, Zhangfeng & Yan, Wenjun [Show all 12 contributors for this article] (2020). Selective Conversion of CO2 into Propene and Butene. Chem. ISSN 2451-9308. 6(12), p. 3344–3363. doi: 10.1016/j.chempr.2020.09.025.
• Yang, Huanhuan; Cui, Xiaojing; Li, Shiying; Cen, Youliang; Deng, Tiansheng & Wang, Jianguo [Show all 8 contributors for this article] (2020). Developing a general method for encapsulation of metal oxide nanoparticles in mesoporous silica shell by unraveling its formation mechanism. Microporous and Mesoporous Materials. ISSN 1387-1811. 305. doi: 10.1016/j.micromeso.2020.110381.
• Kømurcu, Mustafa; Lazzarini, Andrea; Kaur, Gurpreet; Borfecchia, Elisa; Øien-Ødegaard, Sigurd & Gianolio, Diego [Show all 9 contributors for this article] (2020). Co-catalyst free ethene dimerization over Zr-based metal-organic framework (UiO-67) functionalized with Ni and bipyridine. Catalysis Today. ISSN 0920-5861. doi: 10.1016/j.cattod.2020.03.038. Full text in Research Archive
• Pappas, Dimitrios; Kvande, Karoline; Kalyva, Maria Evangelou; Dyballa, Michael Martin; Lomachenko, Kirill A. & Arstad, Bjørnar [Show all 11 contributors for this article] (2020). Influence of Cu-speciation in mordenite on direct methane to methanol conversion: Multi-Technique characterization and comparison with NH3 selective catalytic reduction of NOx. Catalysis Today. ISSN 0920-5861. p. 1–7. doi: 10.1016/j.cattod.2020.06.050. Full text in Research Archive Show summary

  The direct conversion of methane to methanol has the potential of substantially reducing methane emissions and flaring, as such a process might provide an alternative for remote natural gas locations. In this report, we investigate the performance of a range of Cu-exchanged mordenite zeolites as active materials for such a reaction, employing a stepwise protocol comprising activation in oxygen, methane loading, and methanol extraction with steam. We employ in situ HERFD XANES, FT-IR spectroscopy with CO as probe molecule, and XPS to investigate the Cu species in the zeolites during the process. The activity of the materials is investigated both for methane to methanol conversion and NH3 Selective Catalytic Reduction of NOx. It is demonstrated that, despite the fact that the same zeolite materials are active both for NH3-SCR and direct methane to methanol conversion, the active site requirements for these two reactions are different.

• Wang, Sen; Wang, Pengfei; Shi, Dezhi; He, Shipei; Zhang, Li & Yan, Wenjun [Show all 12 contributors for this article] (2020). Direct Conversion of Syngas into Light Olefins with Low CO2 Emission. ACS Catalysis. ISSN 2155-5435. 10(3), p. 2046–2059. doi: 10.1021/acscatal.9b04629.
• Øien-Ødegaard, Sigurd; Bazioti, Kalliopi; Redekop, Evgeniy; Prytz, Øystein; Lillerud, Karl Petter & Olsbye, Unni (2020). A toroidal Zr70 oxysulfate cluster and its diverse packing structures. Angewandte Chemie International Edition. ISSN 1433-7851. 59, p. 21397–21402. doi: 10.1002/anie.202010847. Full text in Research Archive
• Gutterød, Emil Sebastian; Pulumati, S.H.; Kaur, Gurpreet; Lazzarini, Andrea; Solemsli, Bjørn Garding & Gunnæs, Anette Eleonora [Show all 13 contributors for this article] (2020). Influence of Defects and H2O on the Hydrogenation of CO2 to Methanol over Pt Nanoparticles in UiO-67 Metal-Organic Framework. Journal of the American Chemical Society. ISSN 0002-7863. 142(40), p. 17105–17118. doi: 10.1021/jacs.0c07153. Full text in Research Archive
• Lee, Daniel Wolseop; Didriksen, Terje; Olsbye, Unni; Blom, Richard & Grande, Carlos Adolfo (2020). Shaping of metal-organic framework UiO-66 using alginates: Effect of operation variables. Separation and Purification Technology. ISSN 1383-5866. 235, p. 1–12. doi: 10.1016/j.seppur.2019.116182. Full text in Research Archive Show summary

  Shaping of metal-organic frameworks into macro-structured particles for reactors and separation processes is a fundamental step in their way towards commercialization. Extrusion techniques which are used for shaping many porous materials resulted in significant reduction of surface area in many MOF materials and thus alternative techniques are required. One alternative way to shape soft materials is to use a technique coming from molecular gastronomy and biology; the calcium alginate method. For this method, a slurry of the porous material and sodium alginate is prepared and then dropwise put in contact with calcium chloride solution forming spheres. Forming particles with both suitable diffusion and mechanical properties and without significant reductions in surface area, many operating variables must be tuned and optimized. This publication presents the results obtained showing the effects of varying several process variables of the alginate method for shaping UiO-66 MOF. Characterization in terms of surface area and other surface methods, force required to break particles (crushing strength) and measurement of isotherms of carbon dioxide. With this method we have produced MOF particles with crushing strength similar to alumina or silica) and with only 10% of reduction in surface area and adsorption capacity.

• Goodarzi, Farnoosh; Pinilla Herrero, Irene; Kalantzopoulos, Georgios N.; Svelle, Stian; Lazzarini, Andrea & Beato, Pablo [Show all 8 contributors for this article] (2020). Synthesis of mesoporous ZSM-5 zeolite encapsulated in an ultrathin protective shell of silicalite-1 for MTH conversion. Microporous and Mesoporous Materials. ISSN 1387-1811. 292. doi: 10.1016/j.micromeso.2019.109730. Full text in Research Archive
• Ahoba-Sam, Christian; Borfecchia, Elisa; Lazzarini, Andrea; Bugaev, Aram L.; Isah, Abdulrahman Adamu & Taoufik, Mostafa [Show all 8 contributors for this article] (2020). On the conversion of CO2 to value added products over composite PdZn and H-ZSM-5 catalysts: excess Zn over Pd, a compromise or a penalty? Catalysis Science & Technology. ISSN 2044-4753. 10, p. 4373–4385. doi: 10.1039/d0cy00440e. Full text in Research Archive
• Redekop, Evgeniy; Lazzarini, Andrea; Bordiga, Silvia & Olsbye, Unni (2020). A temporal analysis of products (TAP) study of C2-C4 alkene reactions with a well-defined pool of methylating species on ZSM-22 zeolite. Journal of Catalysis. ISSN 0021-9517. 385, p. 300–312. doi: 10.1016/j.jcat.2020.03.020. Full text in Research Archive
• Kvande, Karoline; Pappas, Dimitrios; Dyballa, Michael Martin; Buono, Carlo; Signorile, Matteo & Borfecchia, Elisa [Show all 13 contributors for this article] (2020). Comparing the Nature of Active Sites in Cu-loaded SAPO-34 and SSZ-13 for the Direct Conversion of Methane to Methanol. Catalysts. ISSN 2073-4344. 10(191). doi: 10.3390/catal10020191. Full text in Research Archive Show summary

  On our route towards a more sustainable future, the use of stranded and underutilized natural gas to produce chemicals would be a great aid in mitigating climate change, due to the reduced CO2 emissions in comparison to using petroleum. In this study, we investigate the performance of Cu-exchanged SSZ-13 and SAPO-34 microporous materials in the stepwise, direct conversion of methane to methanol. With the use of X-ray absorption spectroscopy, infrared (in combination with CO adsorption) and Raman spectroscopy, we compared the structure–activity relationships for the two materials. We found that SSZ-13 performed significantly better than SAPO-34 at the standard conditions. From CH4-TPR, it is evident that SAPO-34 requires a higher temperature for CH4 oxidation, and by changing the CH4 loading temperature from 200 to 300 ◦C, the yield (µmol/g) of SAPO-34 was increased tenfold. As observed from spectroscopy, both three- and four-fold coordinated Cu-species were formed after O2-activation; among them, the active species for methane activation. The Cu speciation in SAPO-34 is distinct from that in SSZ-13. These deviations can be attributed to several factors, including the different framework polarities, and the amount and distribution of ion exchange sites.

• Gutterød, Emil Sebastian; Lazzarini, Andrea; Fjermestad, Torstein; Kaur, Gurpreet; Manzoli, Maela & Bordiga, Silvia [Show all 12 contributors for this article] (2019). Hydrogenation of CO2 to Methanol by Pt Nanoparticles Encapsulated in UiO-67: Deciphering the Role of the Metal−Organic Framework. Journal of the American Chemical Society. ISSN 0002-7863. 142. doi: 10.1021/jacs.9b10873. Full text in Research Archive Show summary

  Metal-organic frameworks (MOFs) show great prospect as catalysts and catalyst support materials. Yet, studies that address their dynamic, kinetic and mechanistic role in target reactions are scarce. In this study, an exceptionally stable MOF catalyst consisting of Pt nanoparticles (NPs) embedded in a Zr-based UiO-67 MOF was subject to steady-state and transient kinetic studies involving H/D and 13C /12C exchange, coupled with operando infrared spectroscopy and density functional theory (DFT) modeling, targeting methanol formation from CO2/H2 feeds at 170 C and 1-8 bar pressure. The study revealed that methanol is formed at the interface between the Pt NPs and defect Zr nodes, via formate species attached to the Zr nodes. Methanol formation is mechanistically separated from the formation of co-products CO and methane, except for hydrogen activation on the Pt NPs. Careful analysis of transient data revealed that the number of intermediates was higher than the number of open Zr sites in the MOF lattice around each Pt NP. Hence, additional Zr sites must be available to formate formation. DFT modelling revealed that Pt NP growth is sufficiently energetically favored to enable displacement of linkers and creation of open Zr sites during pretreatment. However, linker displacement during formate formation is energetically disfavored, in line with the excellent catalyst stability observed experimentally. Overall, the study provides firm evidence that methanol is formed at the interface of Pt NPs and linker-deficient Zr6O8 nodes resting on the Pt NP surface.

• Zhang, Lina; Liu, Haiyan; Yue, Yuanyuan; Olsbye, Unni & Bao, Xiaojun (2019). Design and: In situ synthesis of hierarchical SAPO-34@kaolin composites as catalysts for methanol to olefins. Catalysis Science & Technology. ISSN 2044-4753. 9(22), p. 6438–6451. doi: 10.1039/c9cy01663e.
• Lomachenko, Kirill A.; Martini, A; Pappas, Dimitrios; Negri, Chiara; Dyballa, Michael Martin & Berlier, Gloria [Show all 12 contributors for this article] (2019). The impact of reaction conditions and material composition on the stepwise methane to methanol conversion over Cu-MOR: An operando XAS study. Catalysis Today. ISSN 0920-5861. 336, p. 99–108. doi: 10.1016/j.cattod.2019.01.040.
• Dyballa, Michael Martin; Thorshaug, Knut; Pappas, Dimitrios; Borfecchia, Elisa; Kvande, Karoline & Bordiga, Silvia [Show all 12 contributors for this article] (2019). Zeolite surface methoxy groups as key intermediates in the stepwise conversion of methane to methanol. ChemCatChem. ISSN 1867-3880. 11(20), p. 5022–5026. doi: 10.1002/cctc.201901315. Full text in Research Archive Show summary

  This contribution clarifies the overoxidation-preventing key step in the methane-to-methanol (MTM) conversion over copper mordenite zeolites. We followed the methane-to-methanol conversion over copper mordenite zeolites by NMR spectroscopy supported by DRIFTS to show that surface methoxy groups (SMGs) located at zeolite Brønsted sites are the key intermediates. The SMGs with chemical shift of 59 ppm are identical to those formed on a copper-free reference zeolite after reaction with methanol and react with water, methanol, or carbon monoxide to yield methanol, dimethyl ether, and acetate. This reactivity corroborates the location of SMGs at Brønsted sites. We find no evidence for stable SMGs directly at copper sites and explain mechanistically why H-form mordenites outperform their Na-form analogues. This finding is of interest for any future process that tries to trap the intermediate methane oxidation product towards methanol.

• Ahoba-Sam, Christian; Westgård Erichsen, Marius & Olsbye, Unni (2019). Ethene and butene oligomerization over isostructural H-SAPO-5 and H-SSZ-24: Kinetics and mechanism. Cuihuà xuébào. ISSN 0253-9837. 40(11), p. 1766–1777. doi: 10.1016/S1872-2067(19)63426-1. Show summary

  Brønsted-acidic zeolite and zeotype materials are potential catalysts for the conversion of ethene to higher alkenes. In this study, two materials with AFI structure but different acid strength, H-SAPO-5 and H-SSZ-24, were subject to studies of ethene, cis-2-butene and ethene-butene mixture conversion under conditions where C3-C5 alkene formation is thermodynamically favoured over higher hydrocarbons (673–823 K, 1 atm). Ethene and cis-2-butene partial pressures were varied in the range 9–60 and 0.9–8.1 kPa, respectively, and contact times were varied in the range 3.78–756 and 0.573–76.4 s.µmol H+/cm3 over H-SAPO-5 and H-SSZ-24, respectively. Less than 1% conversion of ethene and less than 10% conversion of butene was obtained in the range of conditions used for elucidation of rate parameters. The ethene conversion rates were more than an order of magnitude higher over the more acidic H-SSZ-24 than over H-SAPO-5 (6.5 vs. 0.3 mmol/mol H+.s at 748 K, Pethene = 33 kPa), with corresponding lower reaction order in ethene (1.5 vs. 2.0 at 673 K) and lower apparent activation energy (52 vs. 80 kJ/mol at 698–823 K). Propene selectivity was substantially higher over H-SSZ-24 than over H-SAPO-5 (68% vs. 36% at 0.5% ethene conversion). A similar difference in apparent reaction rates was observed for cis-2-butene conversion over the two catalysts, and for co-feeds of ethene and cis-2-butene. However, the cis-2-butene conversion to C3-C5 alkenes was found to be severely influenced by thermodynamic limitations, impeding a detailed kinetic analysis, and leading predominantly to isobutene formation at the highest temperatures.

• Liu, Ping; Redekop, Evgeniy; Gao, Xiang; Liu, Wen-Chi; Olsbye, Unni & Somorjai, Gabor (2019). Oligomerization of Light Olefins Catalyzed by Brønsted-Acidic Metal–Organic Framework-808. Journal of the American Chemical Society. ISSN 0002-7863. 141(29), p. 11557–11564. doi: 10.1021/jacs.9b03867.
• Kaur, Gurpreet; Øien-Ødegaard, Sigurd; Lazzarini, Andrea; Chavan, Sachin Maruti; Bordiga, Silvia & Lillerud, Karl Petter [Show all 7 contributors for this article] (2019). Controlling the Synthesis of Metal−Organic Framework UiO-67 by Tuning Its Kinetic Driving Force. Crystal Growth & Design. ISSN 1528-7483. 19(8), p. 4246–4251. doi: 10.1021/acs.cgd.9b00916. Full text in Research Archive Show summary

  The successful synthesis of metal−organic framework (MOF) compounds relies on an intricate interplay between the components of the synthesis liquor at the given synthesis conditions. Herein, we explore the interdependence of modulator, linker, and solvent amounts in the synthesis of the Zr-based MOF, UiO-67. Our study suggests that control of linker vacancy defects in UiO-67 is feasible by tuning the ratios of these components, and that such control derives from recognizing the kinetic driving forces during MOF crystal growth. Importantly, we show that linker vacancy defects (and modulator molecules occupying linker sites) can be reduced by limiting the solvent amount to maintain a saturated concentration of linker throughout the synthesis. The method enables formation of UiO-67 with an ideal 1:1 ratio between Zr and the 4,4′-biphenyldicarboxylic acid linker, without surplus linker in the mother liquor or additional postsynthetic steps, and reduces the amount of dimethylformamide (DMF) solvent to less than 20% the amount in previously reported procedures.

• Filez, Matthias; Redekop, Evgeniy; Dendooven, Jolien; Ramachandran, Ranjith K.; Solano, Eduardo & Olsbye, Unni [Show all 11 contributors for this article] (2019). Formation and functioning of bimetallic nanocatalysts: The power of X-ray probes. Angewandte Chemie International Edition. ISSN 1433-7851. p. 1–12. doi: 10.1002/anie.201902859. Full text in Research Archive
• Bugaev, Aram L.; Skorynina, Alina A.; Braglia, Luca; Lomachenko, Kirill A.; Guda, Alexander & Lazzarini, Andrea [Show all 11 contributors for this article] (2019). Evolution of Pt and Pd species in functionalized UiO-67 metal-organic frameworks. Catalysis Today. ISSN 0920-5861. 336, p. 33–39. doi: 10.1016/j.cattod.2019.03.054. Full text in Research Archive

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• Cordero Lanzac, Tomas; Ramirez, Adrian; Cruz-Fernandez, Marta; Zander, Hans-Jörg; Joensen, Finn & Meiswinkel, Andreas [Show all 8 contributors for this article] (2023). Kinetic model, process design and LCA of a CO2 valorization plant to produce light hydrocarbon using a PdZn/ZrO2 + SAPO-34 catalyst.
• Rama, Raquel J.; Nova, Ainara & Olsbye, Unni (2023). Synthesis of linker-based bifunctional ligands for UiO-67 metal-organic frameworks.
• Sannes, Dag Kristian; Øien-Ødegaard, Sigurd; Aunan, Erlend; Nova Flores, Ainara & Olsbye, Unni (2023). Quantification of linker defects in UiO-type metal-organic frameworks.
• Cordero-Lanzac, Tomas; Ramirez, Adrian; Cruz-Fernandez, Marta; Zander, Hans-Jörg; Joensen, Finn & Meiswinkel, Andreas [Show all 8 contributors for this article] (2023). Kinetic model, process design and LCA of a CO2 valorization plant to produce light hydrocarbon using a PdZn/ZrO2 + SAPO-34 catalyst.
• Olsbye, Unni (2023). Thermo-catalytic conversion of CO2 and H2 to higher hydrocarbons.
• Cao, Ning; Nova, Ainara; Olsbye, Unni & Balcells, David (2022). Structural characterization of Cu-UiO MOFs by DFT methods.
• Sannes, Dag Kristian; Øien-Ødegaard, Sigurd; Aunan, Erlend; Nova, Ainara & Olsbye, Unni (2022). Reliable determination of linker defects in UiO-type metal-organic frameworks.
• Sannes, Dag Kristian; Øien-Ødegaard, Sigurd; Aunan, Erlend; Nova, Ainara & Olsbye, Unni (2022). Reliable determination of linker defects in UiO-type metal-organic frameworks.
• Olsbye, Unni (2022). Oxygenate-mediated conversion of CO2 to light olefins and fuels - fundamental and applied aspects.
• Olsbye, Unni (2022). Selective partial oxidation of methane – status and outlook .
• Olsbye, Unni (2022). Kinetic and mechanistic studies of thermocatalytic reactions in dense and nanoporous catalysts.
• Olsbye, Unni (2022). Omdanning av CO2 til drivstoff, plastråstoff og kjemikalier Prosesser og livsløpsanalyser.
• Olsbye, Unni (2022). Site - structure - performance correlations in zeolite- and MOF-based catalysts.
• Olsbye, Unni (2022). Elucidation of mechanistic details of catalytic reactions in nanoporous materials by a combined experimental - computational approach.
• Olsbye, Unni (2022). Studies of diffusion and acid-catalyzed reactions in zeolites and zeotypes.
• Redekop, Evgeniy; Shostak, Vladyslav; Langberg, Geir Severin; Grønås, Terje; Constales, Denis & Galvita, Vladimir V. [Show all 9 contributors for this article] (2021). Recent software developments for high throughput Temporal Analysis of Products (TAP) experiments and simulations.
• Cordero Lanzac, Tomas; Ramirez, Adrian & Olsbye, Unni (2021). The tandem approach to conversion of CO2 and H2 to light hydrocarbons .
• Olsbye, Unni; Gutterød, Emil Sebastian; Lazzarini, Andrea; Fjermestad, Torstein; Pulumati, S.H. & Nova, Ainara [Show all 7 contributors for this article] (2021). Mechanistic studies of CO2 hydrogenation to methanol, methane and CO over Pt-containing Zr-MOFs .
• Olsbye, Unni (2021). Site - structure - performance correlations in zeolite- and MOF-based catalysts.
• Olsbye, Unni (2020). CCU - Considering a greenhouse gas as industrial carbon source.
• Arstad, Bjørnar; Dyballa, Michael Martin; Thorshaug, Knut; Pappas, Dimitrios K; Borfecchia, Elisa & Kvande, Karoline [Show all 12 contributors for this article] (2020). Solid State NMR studies of the stepwise transformation of methane to methanol over Cu-Zeolites.
• Alireza, Hassani; Hansen, Eddy Walther; Olsbye, Unni & Fredriksen, Siw Bodil (2020). Segmental Orientation and Mobility of Ultra-high Molecular Weight Polyethylene . Show summary

  Abstract: Formation of entanglements in Ultra-High Molecular Weight Polyethylene (UHMWPE with average molecular weight exceeding 10^6 g.mol-1 limits their processability [1]. Entanglement characterization techniques mostly requires processing of nascent reactor powder, by melting. This will, however disturb the initial properties, and accordingly, the initial entanglement density in polymers. Therefore, Nuclear Magnetic Resonance (NMR) is an interesting alternative technique where the properties of UHMWPE can be explored in the solid state. However, during relevant NMR studies, the samples were either melted or exposed to time-intensive 13C high field NMR experiments [2]. Recently, simple low field, time-domain NMR with no need for isotope labeling, is gaining attention [3]. The aim of this study is to detect local mobility and orientation of chains across UHMWPE semi-crystalline network, in the solid state. The transverse relaxation time (T2) is determined from the Free Induction Decay (FID) of samples synthesized during controlled catalytic Polymerisation. The method is used to detect differences in dynamic behaviour of UHMWPE samples by mapping the crystalline/amorphous topology [3]. However, due to inhomogeneity in the magnetic field, obtaining detailed information about local chain diffusion is difficult with said experiment. Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence is designed to overcome this issue by refocusing the dephased magnetization in the transverse plane [4]. Thus, CPMG will be used for accurate measurement of the T2 distribution in UHMWPE samples at temperatures between 40-120 °C (below melting temperature). References: [1] A. Pawlak, "The Entanglements of Macromolecules and Their Influence on the Properties of Polymers," Macromolecular Chemistry and Physics, vol. 220, no. 10, p. 1900043, 2019. [2] Y. Yao, S. Jiang, and S. Rastogi, "13C Solid State NMR Characterization of Structure and Orientation Development in the Narrow and Broad Molar Mass Disentangled UHMWPE," Macromolecules, vol. 47, no. 4, pp. 1371-1382, 2014. [3] R. Bärenwald et al., "Local flips and chain motion in polyethylene crystallites: a comparison of melt-crystallized samples, reactor powders, and nanocrystals," Macromolecules, vol. 47, no. 15, pp. 5163-5173, 2014. [4] A. K. Whittaker, T. Bremner, and F. O. Zelaya, "The effect of field inhomogeneities and molecular diffusion on the NMR transverse relaxation behaviour of polymer melts," Polymer, vol. 36, no. 11, pp. 2159-2164, 1995.

• Flatval, Jonas; Berg, Henriette Engen; Lillerud, Karl Petter; Olsbye, Unni; Nielsen, Claus Jørgen & Wilson, Steven Ray Haakon [Show all 7 contributors for this article] (2020). Retention of nitramines on UiO-66 ZrMOF materials and silica-based reversed phase materials .
• Andersen, Kari Anne; Flatval, Jonas; Mrša, Ago; Berg, Henriette Engen; Chavan, Sachin Maruti & Olsbye, Unni [Show all 8 contributors for this article] (2020). Metal organic framework material UiO-66 as a stationary phase in liquid chromatography. Show summary

  Metal organic framework materials (MOFs) are interesting candidates for applications in multiple disciplines, where chromatography is one of the fields where possible applications might exist. The porous structure and large surface area are key features that make MOFs potential candidates for future stationary phases. In the present study, the MOF UiO-66 has been investigated as a stationary phase in a nano-liquid chromatography (LC) system. UiO-66 is composed of zirconium oxide ion nodes and benzene dicarboxylate (BDC) linkers which form a face-centred cubic structure with octahedral pores (opening 6 Å, cavity 11 Å) and tetrahedral pores (opening 6 Å, cavity 7.5 Å) in a 1+2 ratio. Figure adapted from Cliffe et al., Nature communications volume 5 (2014)1. Columns with a 100 µm inner diameter have been packed in-house and tested in a simple LC-UV system for several test substances. The UiO-66 particles pack rapidly and yield columns with low back pressure. We observe reversed phase selectivity, but our experimental data also suggest other interaction mechanisms, phosphate group adsorption to zirconium oxide nodes among them.

• Redekop, Evgeniy; Johansson, Niclas; Kokkonen, Esko; Kalyva, Maria Evangelou; Urpelainen, Samuli & Diplas, Spyridon [Show all 7 contributors for this article] (2019). Pt-Cu nanoparticles on 2D and 3D supports: an AP-XPS/TAP study.
• Gerz, Isabelle; Olsbye, Unni; Tilset, Mats & Amedjkouh, Mohamed (2019). Biomimetic Copper Complexes for Incorporation into MOFs.
• Ahoba-Sam, Christian & Olsbye, Unni (2019). On conversion of CO2 to value added products over a composite PdZn-ZSM-5 catalyst: a compromise or a penalty?
• Olsbye, Unni (2019). Catalytic conversion of gas phase molecules over UiO-67 Zr-MOFs - Two case studies.
• Redekop, Evgeniy; Johansson, Niclas; Kokkonen, Esko; Urpelainen, Samuli; Kalyva, Maria Evangelou & Affolter, Christopher [Show all 8 contributors for this article] (2019). X-Ray spectroscopies and time-resolved kinetics for advanced characterization of heterogeneous catalysts .
• Redekop, Evgeniy; Johansson, Niclas; Urpelainen, Samuli; Kalyva, Maria Evangelou; Affolter, Christopher & Kokkonen, Esko [Show all 10 contributors for this article] (2019). Combining transient kinetics with surface characterization to better understand complex catalytic materials.
• Kalyva, Maria Evangelou; Redekop, Evgeniy; Johansson, Niclas; Urpelainen, Samuli; Gunnæs, Anette Eleonora & Diplas, Spyridon [Show all 7 contributors for this article] (2019). AP-XPS study of bimetallic PtCu nanoparticles supported on SiO2 films.
• Johansson, Niclas; Redekop, Evgeniy; Olsbye, Unni & Urpelainen, Samuli (2019). TAPXPS: A novel approach to APXPS methodology.
• Sunding, Martin Fleissner; Jensen, Ingvild Julie Thue; Svenum, Ingeborg-Helene; Ivashenko, Oleksii; Redekop, Evgeniy & Wells, Justin [Show all 11 contributors for this article] (2019). National Surface and Interface Analysis Laboratory (NICE II): From (near) in-situ to operando XPS analysis.
• Redekop, Evgeniy; Johansson, Niclas; Kalyva, Maria Evangelou; Urpelainen, Samuli; Diplas, Spyridon & Olsbye, Unni (2019). Is Temporal Analysis of Products (TAP) an operando technique? – – Challenges and opportunities of coupling TAP with surface spectroscopies .
• Gutterød, Emil Sebastian & Olsbye, Unni (2019). CO2 Hydrogenation over Pt-Functionalized UiO-67 Zr-MOFs.
• Kømurcu, Mustafa; Lazzarini, Andrea; Kaur, Gurpreet; Borfecchia, Elisa; Øien-Ødegaard, Sigurd & Gianolio, Diego [Show all 9 contributors for this article] (2019). Co-catalyst free ethene dimerization over Zr-based metal-organic framework (UiO-67) functionalized with Ni and bipyridine.
• Olsbye, Unni (2019). Natural Gas Conversion in Microporous Catalysts, Zeotypes and Metal Organic Frameworks.
• Olsbye, Unni (2019). Zeolite catalysis - what can we learn from Temporal Analysis of Products (TAP) experiments?
• Kømurcu, Mustafa; Olsbye, Unni & Lillerud, Karl Petter (2021). Tailoring solid catalysts for the ethene oligomerization reaction. Universitetet i Oslo, Det matematisk-naturvitenskapelige fakultet. ISSN 1501-7710. 2021(2392). Show summary

  The selective oligomerization of ethene to linear alpha olefins is an attractive method for production of a wide range of key intermediates for the chemical industry. Current industrial processes are predominantly utilizing homogenous metal catalysts with a cocatalyst in organic solvents. Heterogeneous catalysts potentially offer a more environmentally friendly alternative and significant effort, both in academia and industry, has been put into the development of heterogeneous catalysts for the ethene oligomerization reaction. In this thesis, nickel functionalized zeolites, silica, and metal-organic framework (MOF) catalysts have been investigated for the cocatalyst free ethene oligomerization reaction. Zeolites and MOFs are porous materials with a wide range of potential use and have numerous applications in catalysis. Different zeolites and MOFs have been investigated to understand the nature of the active site, reaction mechanism and the role of the support in the reaction. This thesis provides insights into role of the zeolites in the reaction and the dynamic nature of the nickel active site during the reaction. Kinetic, spectroscopic, and theoretical methods elucidate the nature of active and spectator nickel species in Ni-MOFs and opens new research opportunities to develop cocatalyst free MOF catalyst.

• Gutterød, Emil Sebastian; Olsbye, Unni; Svelle, Stian & Redekop, Evgeniy (2020). On the hydrogenation of CO2 over Pt-functionalized UiO-67 Metal-Organic Frameworks. Matematisk Naturvitenskapelig fakultet, Universitetet i Oslo. ISSN 1501-7710. 2020(2252).
• Flatval, Jonas; Lundanes, Elsa; Wilson, Steven Ray Haakon; Olsbye, Unni; Nielsen, Claus Jørgen & Berg, Henriette Engen (2020). Retention of nitramines on silica-based reversed phase materials and UiO-66 MOF materials. Universitetet i Oslo. Show summary

  Capturing and storing of CO2 can reduce the emissions of CO2 in the atmosphere. However, such facilities may emit amines that can be transformed into the potentially carcinogenic nitramines dimethylnitramine (DMA-NO2), monoethanolnitramine (MEA-NO2) and monomethylnitramine (MMA-NO2) which may be released into the environment. Presently, methods for trace determination of these compounds are lacking. The goal of the study was to find a material that can give sufficient retention to provide an enrichment of the nitramines before liquid chromatography electrospray ionization-mass spectrometry determination. The retention of the nitramines was examined on various C18 materials and the metal-organic frameworks UiO-66 and UiO-66 1,4-benzenedicarboxylate-NH2 (UiO-66-NH2), which were packed in 100 µm inner diameter columns. Of the tested materials, UiO-66-NH2 showed the highest retention factors for the nitramines. UiO-66-NH2 with 0.1% formic acid adjusted to pH 7 as mobile phase gave the best compromise of retention factors for DMA-NO2 and MEA-NO2, as the intended liquid chromatography-mass spectrometry method was evaluated for DMA-NO2 and MEA-NO2 only. MMA-NO2 had the highest retention factor on UiO-66-NH2 with 0.05% dibutylamine in the mobile phase. In conclusion, the retention factors achieved were in general higher on the UiO-66 materials than on the C18 materials. However, the retention obtained is probably not large enough to give limit of quantification down to 4 ng/L, albeit, not tested, due to extraordinary circumstances.

• Andersen, Kari Anne; Lundanes, Elsa; Berg, Henriette Engen; Wilson, Steven Ray Haakon; Chavan, Sachin Maruti & Lillerud, Karl Petter [Show all 7 contributors for this article] (2020). UiO-66 metal-organic framework materials as stationary phases in liquid chromatography. Universitetet i Oslo. Show summary

  The metal-organic frameworks (MOFs) UiO-66 and UiO-66-NH2 are composed of zirconium oxide nodes (Zr6O4(OH)4(CO2)12)and benzene-1,4-dicarboxylate (BDC) linkers for UiO-66, and the amino-functionalised linker 2-amino-benzene-1,4-dicarboxylate (ABDC) for UiO-66-NH2. UiO-66 and UiO-66-NH2 have large surface areas and a defined pore size and are thus attractive materials for chromatographic separations. The structure of these MOFs also meansseveral retention mechanisms could influence the separation simultaneously, making the retention of functionalised organic molecules on these materials challenging to predict. Hence, the aim of this thesiswas to investigate the chromatography of selected compounds on UiO-66 and UiO-66-NH2 in liquid chromatography (LC), to learn more about the potential applications of these UiO materials.UiO-66 and UiO-66-NH2 particles were packed into 100 μm inner diameter (ID) capillaries, and a simple LC-UV system was used for testing. Both materials rapidly (<30 min) packed into columns of circa 10 cm and provided pressures < 300 bar when used in LC systems. The efficiency (plate height) of the UiO-66-and UiO-66-NH2-columnswerefound to be 18 μm and 199 μm, respectively, using uracil asa modelanalyte. However, phosphate-containing analytes were found to have severe tailing. With an aqueous mobile phase, the retention of a selection of small hydrophilic molecules was found to increase with decreasing organic component in the mobile phase. The flow rate was also found to affect retention factors, with larger retention factors for lower flowrates. The effect of temperature in the range 25–55°C appeared to follow the expected trend of decreasing retention with increasing temperature for the chosen model substances, benzene, ethylbenzene and butylbenzene.Pore volume accessibility studies wereinconclusive. However, observations made strongly suggest that benzene, ethylbenzene, propylbenzene, butylbenzene, naphthalene and phenanthrene were able to access the pores of UiO-66.In conclusion, the UiO-66 MOF materials have chromatographic properties different from thoseof the more common LC separation materials, notably in the ability to retain small polar molecules. However, more research is needed to better understand the retention mechanisms of the materials and to single out application areas for these materials in LC.

• Solemsli, Bjørn Gading; Olsbye, Unni; Gunnæs, Anette Eleonora & Gutterød, Emil Sebastian (2020). A Study of Catalytic Pt Nanoparticles inside a Nano-porous Functionalized UiO MOF-matrix for CO2-Hydrogenation . Universitetet i Oslo. Show summary

  Hydrogenation of carbon dioxide hasreceivedincreasingattentionin catalytic research the last decade as a sustainable alternativeforproducing high value chemicals thattodayare produced fromfossil fuels. The aim of this thesis has been two-fold: First, to study Pt nanoparticles formed in various UiO-66 and -67 metal-organic frameworks (MOFs) by Transmission Electron Microscopy (TEM), and second, to study the Pt-containing MOFs as catalysts for the CO2hydrogenation reaction.Three Zr-based UiO-66 MOF and nineUiO-67 MOF samples containing different amountsof functionalized linkers were impregnated withdifferent amounts ofK2PtCl4and reduced in H2at 350 ̊C for 4 hours to form Pt nanoparticles embedded in the MOF matrix.The samples were then testedin a H2/CO2feed at 8 bar and 170 ̊Cfor the hydrogenation reaction. After testing,TEMwas used to investigate the formation of Pt nanoparticles andtheir relationship with the surrounding MOF structure. The study revealed that, despite variable the linkers in the MOF,the conversion of CO2isdominated bythe reverse water-gas shift reaction,suggestingthat the linkers donot partakethe reactions mechanisms. Analysis usingTEMrevealedthat the Pt nanoparticles grow independently of its surroundings inside the MOFs with no observable growth relationshipwith the MOF. The nanoparticles are seen to grow into octahedral crystals that are larger than the pores in the framework. Samples with different amountsof missing linker type defects show that the presence of open Zr-node sitesenhances the selectivity towards methanol. A sample of Pt-functionalized UiO-67 with 10% [2,2’-bipyridine]5,5’-dicaboxylicacidlinker was oxidised toinduce missing linkerdefects post synthetically. After reduction in H2at 350 ̊C for 4 hours, the sample was oxidized in situin synthetic air for three different time spans. Careful analysis with N2-adsroption and TEM revealedthat the structure of the MOF deteriorates and loses accessible surface area with increasing timeon steam, while keeping the dispersion of the Pt nanoparticles. PXRD analysis revealedthe formation of tetragonal ZrO2. Extensive testsfrom 1-30 bar and 170-375 ̊C reveal a lower conversion and higher selectivity towards methanol for a fully calcined sample, indicating that the Zr-nodes behave similarlyto non-MOF ZrO2supports. Transient kinetic studies of the parent UiO-67 sample revealedthat the sample behaves similarlytopreviously studied systemsby Gutterød et al., and showed the presence of an inverse kinetic isotope effect for methane and methanolformation upon H2/D2exchange.

• Sannes, Johnny Andreas; Olsbye, Unni; Kalantzopoulos, Georgios N. & Arstad, Bjørnar (2020). CO2 adsorption and characterization of tailor-made metal-organic frameworks. Universitetet i Oslo. Show summary

  In this work, the 𝐶𝑂2adsorption capacityof chemically interesting metal-organic frameworks (MOFs) have been investigated. The MOFs have been characterized using standard inorganic/organic characterization tools such as pXRD, TGA, liquidand solid state NMR, SEM-EDS, static anddynamic gas adsorption.Potentially strong adsorption sites on the Pt–Zr interface was investigated by the use of TAP. The isosteric heat of adsorption have been estimated for UiO –67 as a function of pretreatment.A comparison of the isosteric heat of adsorption determined by the use of static and dynamic gas adsorption studies have been made.A two-step adsorption mechanismin the N2adsorption isotherm was observed for UiO –67 in the low pressure regime (𝑝𝑝0<0.005). The observed adsorption isothermshow resemblance to that of MOF –808, however occurring at a much lower pressure.UiO –67 and UiO –67 type MOFs have been investigated by the use of ss –NMR. A major effort was made towards the assignment of the peaks in therecorded1H and 13C spectrum of UiO –67. The work was leading to the hopeful elucidation of adsorption sites and adsorption orientations, however due to time constraint only the groundworkhave been performed.

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