Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts

Delir Kheyrollahi Nezhad, Parastoo; Bekheet, Maged F.; Bonmassar, Nicolas; Gili, Albert; Kamutzki, Franz; Gurlo, Aleksander; Doran, Andrew; Schwarz, Sabine; Bernardi, Johannes; Praetz, Sebastian; Niaei, Aligholi; Farzi, Ali; Penner, Simon

doi:10.1039/d1cy02044g

Title: Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts

Journal Article · Thu Jan 06 00:00:00 EST 2022 · Catalysis Science and Technology

DOI:https://doi.org/10.1039/d1cy02044g· OSTI ID:1856514

Delir Kheyrollahi Nezhad, Parastoo ^[1];

^[2]; Bonmassar, Nicolas ^[3];

^[2]; Kamutzki, Franz ^[2]; Gurlo, Aleksander ^[2];

^[4]; Schwarz, Sabine ^[5];

^[5]; Praetz, Sebastian ^[2]; Niaei, Aligholi ^[1];

^[1];

^[3]

Univ. of Tabriz (Iran)
Technische Univ. Berlin (Germany)
Univ. Innsbruck (Austria)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
TU Wien, Vienna (Austria)

To elucidate the role of earth alkaline doping in perovskite-based dry reforming of methane (DRM) catalysts, we embarked on a comparative and exemplary study of a Ni-based Sm perovskite with and without Sr doping. While the Sr-doped material appears as a structure-pure Sm_1.5Sr_0.5NiO₄ Ruddlesden Popper structure, the undoped material is a NiO/monoclinic Sm₂O₃ composite. Hydrogen pre-reduction or direct activation in the DRM mixture in all cases yields either active Ni/Sm₂O₃ or Ni/Sm₂O₃/SrCO₃ materials, with albeit different short-term stability and deactivation behavior. The much smaller Ni particle size after hydrogen reduction of Sm_1.5Sr_0.5NiO₄, and of generally all undoped materials stabilizes the short and long-term DRM activity. Carbon dioxide reactivity manifests itself in the direct formation of SrCO₃ in the case of Sm_1.5Sr_0.5NiO₄, which is dominant at high temperatures. For Sm_1.5Sr_0.5NiO₄, the CO : H₂ ratio exceeds 1 at these temperatures, which is attributed to faster direct carbon dioxide conversion to SrCO₃ without catalytic DRM reactivity. As no Sm₂O₂CO₃ surface or bulk phase as a result of carbon dioxide activation was observed for any material – in contrast to La₂O₂CO₃ – we suggest that oxy-carbonate formation plays only a minor role for DRM reactivity. Rather, we identify surface graphitic carbon as the potentially reactive intermediate. Graphitic carbon has already been shown as a crucial reaction intermediate in metal-oxide DRM catalysts and appears both for Sm_1.5Sr_0.5NiO₄ and NiO/monoclinic Sm₂O₃ after reaction as crystalline structure. It is significantly more pronounced for the latter due to the higher amount of oxygen-deficient monoclinic Sm₂O₃ facilitating carbon dioxide activation. Despite the often reported beneficial role of earth alkaline dopants in DRM catalysis, we show that the situation is more complex. In our studies, the detrimental role of earth alkaline doping manifests itself in the exclusive formation of the sole stable carbonated species and a general destabilization of the Ni/monoclinic Sm₂O₃ interface by favoring Ni particle sintering.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Technische Univ. Berlin (Germany)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Austrian Science Fund (FWF); German Research Foundation (DGR)

Grant/Contract Number:: AC02-05CH11231; EXC 2008/ –390540038.

OSTI ID:: 1856514

Journal Information:: Catalysis Science and Technology, Vol. 12, Issue 4; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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