Computational modelling of carbon dioxide reduction to methanol on heterogeneous zirconia-supported copper catalysts
Tässä väitöskirjassa tarkasteltiin hiilidioksidin vedyttämiseen metanoliksi käytettävien,
heterogeenisten Cu/ZnO/zirkoniakatalyyttien (CZZ) rakennetta ja adsorptio-
ominaisuuksia, käyttäen työvälineenä tiheysfunktionaaliteoriaan (density
functional theory, DFT) perustuvia mallinnusmenetelmiä. Muita matemattisia
malleja, kuten energiavälimallia (energetic span model) ja atomistista termodynamiikkaa,
käytettiin CZZ systeemin kolmen komponentin välisen rajapinnan
katalyyttisen aktiivisuuden ja stabiilisuuden arviointiin.
Sopiva laskennallinen malli kuvaamaan metalli–zirkonia rajapintaa valittiin
laajan seulonnan pohjalta. Sen tulokset osoittavat, kuinka käytetyn nanosauvamallin
rakenne ja yksikkökopin valinnasta aiheutuva jännite johtavat sekä hiilidioksidin
liian voimakkaaseen kiinnittymiseen. Sinkkipromoottorin vaikutusta
tarkasteltiin käyttäen mallia, jossa Cu–zirkonia-rajapintaan seostettiin sinkkiatomeja.
Hiilidioksidin vedytyksen alkeisreaktiot CuZn–ZrO2 mallinnettiin Cu ja
CuZn rajapinnoilla DFT:tä ja energiavälimallia käyttäen. Laskut havainnollistavat,
kuinka Zn keskukset rajapinnalla stabiloivat valikoivasti tiettyjä adsorbaatteja
ja reaktiovälituotteita, kuten CO2, COOH, ja H2CO. Energiavälianalyysin ennakoi
vedytyksen kulkevan nopeiten käänteisen vesikaasun siirtoreaktion ja hiilimonoksidin
vedytyksen kautta. Työssä tutkittiin myös suuresti hajaantuneen
sinkkipromoottorin rakennetta ja hapetus–pelkistysominaisuuksia zirkonian pinnalla.
Laskujen osoittama sinkkioksidimonomeerien ja pienten agglomeraattien
stabiilisuus zirkoniapinnalla viittaa niiden taipumukseen vastustaa suurempien
partikkeleiden kasvua. Atomistinen termodynaaminen tarkastelu vahvistaa, että
zirkonia estää myös sinkkioksidia pelkistymistä täysin, myös reaktio-olosuhteissa.
Tulokset tarjoavat atomitason tietoa sinkkioksidipromoottorin toiminnasta ja vaikutuksesta
hiilidioksidin kiinnittymiseen ja vedytykseen. In this dissertation, computational modelling methods based in density functional
theory (DFT) were used to investigate the structure and adsorption characteristics
of a heterogeneous catalytic system, consisting of zirconia-supported
copper nanoparticles with a zinc oxide promoter (CZZ), that is used for carbon dioxide
conversion to methanol (CTM). Supplementary analysis methods, such as
the energetic span model and atomistic thermodynamics, were used to examine
the stability and catalytic performance of the ternary Cu–Zn(O)–ZrO2 interface.
An extended screening was conducted to establish a suitable computational
model for representing the metal–zirconia interface. Our results demonstrate
how the specific internal geometry of a nanorod model and strains caused by
lattice mismatch between Cu and ZrO2 affect CO2 adsorption at the interface,
even leading to an overestimation of binding strength. The effect of Zn centres
at the active interface sites was examined by using mixed CuZn interfaces and
modelling the full catalytic network of CO2 CTM using DFT and energetic span
analysis. The calculated binding of reaction intermediates demonstrated how
Zn incorporated into the catalyst metal selectively stabilizes certain species, such
as CO2, COOH and H2CO. The energetic span analysis suggests that a reverse
water–gas shift reaction followed by CO hydrogenation is the mechanistic pathway
with the highest turnover frequency. An examination of ZnO monomers
and sub-nano clusters on the zirconia surface suggests that the ZrO2 support offers
some resistance to the initial stages of agglomeration. An atomistic thermodynamics
analysis suggests that the complete reduction of zirconia-bound ZnO
into metallic Zn is unfavourable. Our results offer an atomic-level view of the
behaviour of the ZnO promoter and its effect on CO2 adsorption and conversion.
Publisher
Jyväskylän yliopistoISBN
978-952-86-0360-3ISSN Search the Publication Forum
2489-9003Contains publications
- Artikkeli I: Gell, L., Lempelto, A., Kiljunen, T., & Honkala, K. (2021). Influence of a Cu–zirconia interface structure on CO2 adsorption and activation. Journal of Chemical Physics, 154(21), Article 214707. DOI: 10.1063/5.0049293. JYX: jyx.jyu.fi/handle/123456789/80353
- Artikkeli II: Arandia, A., Yim, J., Warraich, H., Leppäkangas, E., Bes, R., Lempelto, A., Gell, L., Jiang, H., Meinander, K., Viinikainen, T., Huotari, S., Honkala, K., & Puurunen, R. L. (2023). Effect of atomic layer deposited zinc promoter on the activity of copper-on-zirconia catalysts in the hydrogenation of carbon dioxide to methanol. Applied Catalysis B : Environmental, 321, Article 122046. DOI: 10.1016/j.apcatb.2022.122046
- Artikkeli III: Lempelto, A., Gell, L., Kiljunen, T., & Honkala, K. (2023). Exploring CO2 hydrogenation to methanol at a CuZn–ZrO2 interface via DFT calculations. Catalysis Science and Technology, 13(15), 4387-4399. DOI: 10.1039/d3cy00549f
- Artikkeli IV: Lempelto, A., Kauppinen, M., & Honkala, K. (2024). Computational Exploration of Subnano Zn and Cu Species on Cu/ZrO2 : Implications for Methanol Synthesis. Journal of Physical Chemistry C, 128(23), 9492-9503. DOI: 10.1021/acs.jpcc.4c01300. JYX: jyx.jyu.fi/handle/123456789/96017
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