CO<sub>2</sub> Hydrogenation to Methanol on ZnO/ZrO<sub>2</sub> Catalysts: Effects of Zirconia Phase

Lin, Lili; Wang, Guihui; Zhao, Fulin

doi:10.1002/slct.202002108

Cited by 17 publications

(6 citation statements)

References 40 publications

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“…[15] On the other hand, during CO2 TPD measurements, two bands were observed at ~ 314 °C and 480 °C for ZrO2-t-based catalysts, but no bands were observed for the ZrO2-m-based samples, which suggests that ZrO2-t had stronger basic sites for CO2 adsorption (Figure S2b). [16] H2-TPR experiments showed comparable reduction temperatures for ZnO/ZrO2-t and ZnO/ZrO2-m, with a peak of H2 consumption between 300 and 400 °C (Figure S2c). However, the amount of hydrogen consumed in ZnO/ZrO2-m (404.79 μL) was much higher than that of ZnO/ZrO2-t (142.15.79 μL), suggesting that the highly dispersed ZnO in ZnO/ZrO2-t is less reducible due to stronger interaction with ZrO2-t.…”

Section: Resultsmentioning

confidence: 86%

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote the CO2-to-Methanol Reaction

Zhang,

Yu,

Mendes

et al. 2024

Preprint

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ZnO/ZrO2 catalysts have shown excellent activity in the CO2 hydrogenation to methanol compared with single component counterparts, but the interaction between ZnO and ZrO2 is still poorly understood. In particular, the effect of the ZrO2 support phase (tetragonal vs. monoclinic) was not systematically explored. Here, we have synthesized ZnO/ZrO2 catalyst materials supported on tetragonal ZrO2 (ZnO/ZrO2-t) and monoclinic ZrO2 (ZnO/ZrO2-m), which resulted in the formation of different ZnOx species, consisting of sub-nanometer ZnO moieties and large-sized ZnO particles, respectively. ZnO/ZrO2-t exhibited much higher methanol selectivity (81 %) and methanol yield (1.25 mmol/g/h) compared with ZnO/ZrO2-m (39 % and 0.67 mmol/g/h). The difference in performance was attributed to the redox state and degree of dispersion of Zn, based on spectroscopy and microscopy results. Operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in situ near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) showed that ZnO/ZrO2-t had a high density of ZnO-ZrO sites, which favored the formation of active HCOO* species and enhanced the yield and selectivity of methanol along the formate pathway. Operando UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS) together with Raman spectroscopy and high-angle angular dark field-scanning transmission electron microscopy (HAADF-STEM) combined with energy dispersive X-ray (EDX) analysis revealed that on ZnO/ZrO2-t, ZnO clusters were further dispersed during catalysis at 320 °C, forming high density of ZnO-ZrO sites, and facilitating the hydrogenation of CO2 to methanol, while larger ZnO particles on ZnO/ZrO2-m remained stable throughout the reaction. This study shows that the phase of ZrO2 supports can be used to control the dispersion of the active phase and lead to enhanced catalytic performance. We believe the insights are relevant for other methanol synthesis catalysts, where metal-support interactions are pivotal for catalyst activity and stability.

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Section: Resultsmentioning

confidence: 86%

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote the CO2-to-Methanol Reaction

Zhang,

Yu,

Mendes

et al. 2024

Preprint

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“…[79] The opposite shift is observed for ZrO 2 -ZnO, where the Zr 3d and Zn 2p levels appear at higher binding energies, consistent with our observations. [80] The XPS analysis reveals that the deconvoluted Zn 2p 3/2 components ratio is close to unity and does not differ between the powders. From the relative intensities of Zr 3d doublets, approximately half of the surface comprises nonstoichiometric ZrO 2 , which does not change with the annealing conditions.…”

Section: Determination Of the Element Oxidation Statementioning

confidence: 83%

Additive Manufacturing of Zn‐Doped ZrO₂Architectures

Winczewski,

Arriaga‐Dávila,

Maestre

et al. 2024

Adv Eng Mater

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Tailoring the properties of microfabricated ceramics through doping can unlock new avenues for the additive manufacturing (AM) of advanced three‐dimensional (3D) architectures. The first step to achieving optical functionality is to control material morphology, crystallinity, and defects associated with the composition of the produced AM architecture and dopants. For this purpose, AM of zinc‐doped zirconia (ZrO2:Zn) 3D microarchitectures are proposed using two‐photon lithography and tailor‐made resin. It is found that Zn doping modulates ZrO2:Zn architecture crystallinity and optical properties. The modification of optical properties through Zn doping is confirmed by micro‐photoluminescence, where higher energy photon emission is observed due to the promotion of oxygen vacancies and surface defects. It is also shown that Zn 2.5% and 5 wt.% stabilizes the monoclinic ZrO2 at a lower temperature than in the case of undoped ZrO2. Furthermore, we have evidence that Zn tends to form ZnO wurtzite, which is later sublimated. Our findings provide a promising route to understand the role of defects ZrO2:Zn optically upon annealing.This article is protected by copyright. All rights reserved.

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“…Through comparison of amorphous, monoclinic and tetrahedral zirconia, it was observed that a monoclinic-tetragonal mix was beneficial for the reactivity. 230 The differences are attributed to the lattice oxygen content. From a mechanistic point of view, the RWGS pathway is favoured on this kind of catalyst with carbonates and bicarbonates as key intermediates.…”

Section: Co2 To Methanolmentioning

confidence: 99%

Addressing the CO₂ challenge through thermocatalytic hydrogenation to carbon monoxide, methanol and methane

Len

Luque

2023

Green Chem.

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CO₂ Hydrogenation to Methanol on ZnO/ZrO₂ Catalysts: Effects of Zirconia Phase

Cited by 17 publications

References 40 publications

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote the CO2-to-Methanol Reaction

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote the CO2-to-Methanol Reaction

Additive Manufacturing of Zn‐Doped ZrO₂Architectures

Addressing the CO₂ challenge through thermocatalytic hydrogenation to carbon monoxide, methanol and methane

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CO2 Hydrogenation to Methanol on ZnO/ZrO2 Catalysts: Effects of Zirconia Phase

Cited by 17 publications

References 40 publications

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote the CO2-to-Methanol Reaction

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote the CO2-to-Methanol Reaction

Additive Manufacturing of Zn‐Doped ZrO2Architectures

Addressing the CO2 challenge through thermocatalytic hydrogenation to carbon monoxide, methanol and methane

Contact Info

Product

Resources

About

CO₂ Hydrogenation to Methanol on ZnO/ZrO₂ Catalysts: Effects of Zirconia Phase

Additive Manufacturing of Zn‐Doped ZrO₂Architectures

Addressing the CO₂ challenge through thermocatalytic hydrogenation to carbon monoxide, methanol and methane