Michael Martin Dyballa

• Kvande, Karoline; Pappas, Dimitrios; Dyballa, Michael Martin; Buono, Carlo; Signorile, Matteo; Borfecchia, Elisa; Lomachenko, Kirill A.; Arstad, Bjørnar; Bordiga, Silvia; Berlier, Gloria; Olsbye, Unni; Beato, Pablo & Svelle, Stian (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 Fulltekst i vitenarkiv. Vis sammendrag

  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.

• Pappas, Dimitrios; Kvande, Karoline; Kalyva, Maria Evangelou; Dyballa, Michael Martin; Lomachenko, Kirill A.; Arstad, Bjørnar; Borfecchia, Elisa; Bordiga, Silvia; Olsbye, Unni; Beato, Pablo & Svelle, Stian (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.  s 1- 7 . doi: 10.1016/j.cattod.2020.06.050 Vis sammendrag

  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.

• Dyballa, Michael Martin; Thorshaug, Knut; Pappas, Dimitrios; Borfecchia, Elisa; Kvande, Karoline; Bordiga, Silvia; Berlier, Gloria; Lazzarini, Andrea; Olsbye, Unni; Beato, Pablo; Svelle, Stian & Arstad, Bjørnar (2019). Zeolite surface methoxy groups as key intermediates in the stepwise conversion of methane to methanol. ChemCatChem.  ISSN 1867-3880.  11(20), s 5022- 5026 . doi: 10.1002/cctc.201901315 Fulltekst i vitenarkiv. Vis sammendrag

  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.

• Brogaard, Rasmus Yding; Kømurcu, Mustafa; Dyballa, Michael Martin; Botan, Alexandru; Van Speybroeck, Veronique; Olsbye, Unni & De Wispelaere, Kristof (2019). Ethene Dimerization on Zeolite-Hosted Ni Ions: Reversible Mobilization of the Active Site. ACS Catalysis.  ISSN 2155-5435.  9(6), s 5645- 5650 . doi: 10.1021/acscatal.9b00721
• Dyballa, Michael Martin; Pappas, Dimitrios; Kvande, Karoline; Borfecchia, Elisa; Arstad, Bjørnar; Beato, Pablo; Olsbye, Unni & Svelle, Stian (2019). On how copper mordenite properties govern the framework stability and activity in the methane-to-methanol conversion. ACS Catalysis.  ISSN 2155-5435.  9(1), s 365- 375 . doi: 10.1021/acscatal.8b04437
• Holzinger, Julian; Nielsen, Malte; Beato, Pablo; Brogaard, Rasmus Yding; Buono, Carlo; Dyballa, Michael Martin; Falsig, Hanne; Skibsted, Jørgen & Svelle, Stian (2019). Identification of Distinct Framework Aluminum Sites in Zeolite ZSM-23: A Combined Computational and Experimental 27Al NMR Study. Journal of Physical Chemistry C.  ISSN 1932-7447.  123(13), s 7831- 7844 . doi: 10.1021/acs.jpcc.8b06891
• Lomachenko, Kirill A.; Martini, A; Pappas, Dimitrios; Negri, Chiara; Dyballa, Michael Martin; Berlier, Gloria; Bordiga, Silvia; Lamberti, Carlo; Olsbye, Unni; Svelle, Stian; Beato, Pablo & Borfecchia, Elisa (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, s 99- 108 . doi: 10.1016/j.cattod.2019.01.040
• Pappas, Dimitrios; Borfecchia, Elisa; Lomachenko, Kirill A.; Lazzarini, Andrea; Gutterød, Emil Sebastian; Dyballa, Michael Martin; Martini, Andrea; Berlier, Gloria; Bordiga, Silvia; Lamberti, Carlo; Arstad, Bjørnar; Olsbye, Unni; Beato, Pablo & Svelle, Stian (2019). Cu-Exchanged Ferrierite Zeolite for the Direct CH4 to CH3OH Conversion: Insights on Cu Speciation from X-Ray Absorption Spectroscopy. Topics in catalysis.  ISSN 1022-5528.  62(7-11) . doi: 10.1007/s11244-019-01160-7 Vis sammendrag

  The direct stepwise transformation of CH4 to CH3OH over Cu-exchanged zeolites has been an intensively researched reaction as it can provide a solution for the utilization of this abundant feedstock. Up to date a commercial process is far from realization, which is why an understanding of the Cu speciation in zeolites as a function of reaction conditions as well as the development of a mechanistic view of the reaction are necessary to further advance the field. Herein we study Cu-exchanged ferrierite zeolite for the direct CH4 to CH3OH conversion by utilizing X-ray absorption spectroscopy (XAS), in order to assess the local structure and electronic properties of Cu through the reaction. A Cu-FER sample with a Cu/Al = 0.20 and Si/Al = 11 was subjected to three reaction cycles yielding ultimately 96 µmol CH3OH/gzeolite . Normalized to the Cu loading, this accounts for 0.33 mol CH3OH /molCu, making the sample comparable to very active Cu-MOR materials reported in the literature. During O2 activation, a transient self-reduction regime of CuII to CuI ions was identified; eventually leading to mostly framework interacting CuII species. CH4 loading leads to a reduction of these CuII containing species; which are finally partially reoxidized during H2O-assisted CH3OH extraction. The speciation after CH4 activation as well as H2O-assisted CH3OH extraction was assessed via linear combination fitting analysis of the XAS data.

• Borfecchia, Elisa; Pappas, Dimitrios; Dyballa, Michael Martin; Lomachenko, Kirill A.; Negri, Chiara; Signorile, Matteo & Berlier, Gloria (2018). Evolution of active sites during selective oxidation of methane to methanol over Cu-CHA and Cu-MOR zeolites as monitored by operando XAS. Catalysis Today.  ISSN 0920-5861. . doi: 10.1016/j.cattod.2018.07.028
• Dyballa, Michael Martin; Pappas, Dimitrios; Borfecchia, Elisa; Beato, Pablo; Olsbye, Unni; Lillerud, Karl Petter; Arstad, Bjørnar & Svelle, Stian (2018). Tuning the material and catalytic properties of SUZ-4 zeolites for the conversion of methanol or methane. Microporous and Mesoporous Materials.  ISSN 1387-1811.  265, s 112- 122 . doi: 10.1016/j.micromeso.2018.02.004 Fulltekst i vitenarkiv.
• Pappas, Dimitrios; Borfecchia, Elisa; Dyballa, Michael Martin; Lomachenko, Kirill A.; Martini, Andrea; Berlier, Gloria; Arstad, Bjørnar; Lamberti, Carlo; Bordiga, Silvia; Olsbye, Unni; Svelle, Stian & Beato, Pablo (2018). Understanding and optimizing the performance of Cu‐FER for the direct CH4 to CH3OH conversion. ChemCatChem.  ISSN 1867-3880.  11(1), s 621- 627 . doi: 10.1002/cctc.201801542 Fulltekst i vitenarkiv.
• Pappas, Dimitrios; Martini, Andrea; Dyballa, Michael Martin; Kvande, Karoline; Teketel, Shewangizaw; Lomachenko, Kirill A.; Baran, Rafal; Glatzel, Pieter; Arstad, Bjørnar; Berlier, Gloria; Lamberti, Carlo; Bordiga, Silvia; Olsbye, Unni; Svelle, Stian; Beato, Pablo & Borfecchia, Elisa (2018). The nuclearity of the active site for methane to methanol conversion in Cu-mordenite: a quantitative assessment. Journal of the American Chemical Society.  ISSN 0002-7863.  140(45), s 15270- 15278 . doi: 10.1021/jacs.8b08071 Fulltekst i vitenarkiv.
• Pappas, Dimitrios; Borfecchia, Elisa; Dyballa, Michael Martin; Pankin, Ilia A.; Lomachenko, Kirill A.; Martini, Andrea; Signorile, Matteo; Teketel, Shewangizaw; Arstad, Bjørnar; Berlier, Gloria; Lamberti, Carlo; Bordiga, Silvia; Olsbye, Unni; Lillerud, Karl Petter; Svelle, Stian & Beato, Pablo (2017). Methane to methanol: structure-activity relationships for Cu-CHA. Journal of the American Chemical Society.  ISSN 0002-7863.  139(42), s 14961- 14975 . doi: 10.1021/jacs.7b06472 Fulltekst i vitenarkiv.
• Rojo-Gama, Daniel; Nielsen, Malte; Wragg, David; Dyballa, Michael Martin; Holzinger, Julian; Falsig, Hanne; Lundegaard, Lars Fahl; Beato, Pablo; Brogaard, Rasmus Yding; Lillerud, Karl Petter; Olsbye, Unni & Svelle, Stian (2017). A Straightforward Descriptor for the Deactivation of Zeolite Catalyst H-ZSM-5. ACS Catalysis.  ISSN 2155-5435.  7(12), s 8235- 8246 . doi: 10.1021/acscatal.7b02193 Fulltekst i vitenarkiv.

Se alle arbeider i Cristin

• Dyballa, Michael Martin; Pappas, Dimitrios; Borfecchia, Elisa; Kvande, Karoline; Bordiga, Silvia; Berlier, Gloria; Lamberti, Carlo; Arstad, Bjørnar; Beato, Pablo; Olsbye, Unni & Svelle, Stian (2019). Cu-MOR applied in the stepwise methane-to-methanol conversion.
• Kvande, Karoline; Svelle, Stian; Dyballa, Michael Martin & Pappas, Dimitrios (2019). A Study of Cu-loaded SAPO-34 for the Direct Conversion of Methane to Methanol.
• Pappas, Dimitrios; Borfecchia, Elisa; Dyballa, Michael Martin; Berlier, Gloria; Bordiga, Silvia; Olsbye, Unni; Beato, Pablo & Svelle, Stian (2018). FOLLOWING O2-ACTIVATION OF CU-ZEOLITES WITH TIME-RESOLVED XAS.
• Pappas, Dimitrios; Borfecchia, Elisa; Dyballa, Michael Martin; Martini, Andrea; Lomachenko, Kirill A.; Berlier, Gloria; Lamberti, Carlo; Bordiga, Silvia; Olsbye, Unni; Beato, Pablo & Svelle, Stian (2018). Methane to Methanol over Cu-Zeolites: Establishing Structure-Activity Relationships.
• Pappas, Dimitrios; Borfecchia, Elisa; Dyballa, Michael Martin; Lomachenko, Kirill A.; Signorile, Matteo; Berlier, Gloria; Lamberti, Carlo; Bordiga, Silvia; Olsbye, Unni; Lillerud, Karl Petter; Svelle, Stian & Beato, Pablo (2017). Searching for the Active Sites Responsible for the CH4 to CH3OH Conversion over Cu-Chabazite Materials.
• Berlier, Gloria; Borfecchia, Elisa; Negri, C; Bordiga, Silvia; Beato, Pablo; Lomachenko, Kirill A.; Pankin, Ilia; Lamberti, Carlo; Pappas, Dimitrios; Dyballa, Michael Martin; Olsbye, Unni & Svelle, Stian (2017). Comparing small and large pore Cu-zeolites for the partial oxidation of methane to methanol: an operando spectroscopic study.
• Dyballa, Michael Martin; Arstad, Bjørnar; Pappas, Dimitrios; Svelle, Stian; Olsbye, Unni; Beato, Pablo; Bordiga, Silvia & Borfecchia, Elisa (2017). On the preparation of Cu-containing Zeolites - How to avoid comparing Apples to Oranges..
• Pappas, Dimitrios; Borfecchia, Elisa; Dyballa, Michael Martin; Pankin, Ilia A.; Lomachenko, Kirill A.; Martini, Andrea; Signorile, Matteo; Teketel, Shewangizaw; Arstad, Bjørnar; Berlier, Gloria; Lamberti, Carlo; Bordiga, Silvia; Olsbye, Unni; Lillerud, Karl Petter; Svelle, Stian & Beato, Pablo (2017). XAS reveals structure-activity relationships for the Methane-to-Methanol conversion over Cu-zeolites. ESRF Highlights of the Year.  s 49- 51
• Pappas, Dimitrios; Borfecchia, Elisa; Dyballa, Michael Martin; Pankin, Ilia; Lomachenko, Kirill A.; Berlier, Gloria; Arstad, Bjørnar; Lamberti, Carlo; Bordiga, Silvia; Beato, Pablo; Olsbye, Unni & Svelle, Stian (2017). Key Reaction Steps in the Partial Oxidation of Methane to Methanol over Cu-SSZ-13.

Se alle arbeider i Cristin