Enhanced activity, selectivity and stability of a CuO-ZnO-ZrO2 catalyst by adding graphene oxide for CO2 hydrogenation to methanol

Witoon, Thongthai; Numpilai, Thanapa; Phongamwong, Thanaree; Donphai, Waleeporn; Boonyuen, Chaiyan; Warakulwit, Chompunuch; Chareonpanich, Metta; Limtrakul, Jumras

doi:10.1016/j.cej.2017.11.117

Cited by 141 publications

(91 citation statements)

References 42 publications

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“…Zr was added to the support as active reaction sites for surface carbonate formation. The carbonate groups can then react with the atomic hydrogen generated by H2 splitting over Cu to finally form carbon based fuels 20,[23][24][25] . Two types of Cu-Zr-SBA-15 were synthesized.…”

Section: Introductionmentioning

confidence: 99%

Time evolution of the CO2 hydrogenation to fuels over Cu-Zr-SBA-15 catalysts

Atakan

Erdtman

Mäkie

et al. 2018

Journal of Catalysis

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The self-archived postprint version of this journal article is available at Linköping University Institutional Repository (DiVA): http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-147297 N.B.: When citing this work, cite the original publication.Atakan, A., Erdtman, E., Mäkie, P., Ojamäe, L., Odén, M., (2018) ABSTRACT: Time evolution of catalytic CO2 hydrogenation to methanol and dimethyl ether (DME) has been investigated in a hightemperature high-pressure reaction chamber where products accumulate over time. The employed catalysts are based on a nano-assembly composed of Cu nanoparticles infiltrated into a Zr doped SiOx mesoporous framework (SBA-15): Cu-Zr-SBA-15. The CO2 conversion was recorded as a function of time by gas chromatography-mass spectrometry (GC-MS) and the molecular activity on the catalyst's surface was examined by diffuse reflectance in-situ Fourier transform infrared spectroscopy (DRIFTS). The experimental results showed that after 14 days a CO2 conversion of 25% to methanol and DME was reached when a DME selective catalyst was used which was also illustrated by thermodynamic equilibrium calculations. With higher Zr content in the catalyst, greater selectivity for methanol and a total 9.5 % conversion to methanol and DME was observed, yielding also CO as an additional product. The time evolution profiles indicated that DME is formed directly from methoxy groups in this reaction system. Both DME and methanol selective systems show the thermodynamically highest possible conversion.

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Section: Introductionmentioning

confidence: 99%

Time evolution of the CO2 hydrogenation to fuels over Cu-Zr-SBA-15 catalysts

Atakan

Erdtman

Mäkie

et al. 2018

Journal of Catalysis

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“…It can be seen from the Table that the specific surface area of the phase pure IS x C samples are in the range of 20–45 m 2 /g, and the pore volume ranges between ∼0.15–0.30 cm 3 /g. With increase in Zn substitution from 0 % to 50 %, the specific surface area was increased gradually from 20.2 m 2 /g for IS0 C to 45.7 m 2 /g for IS50 C. It is well known that the effective surface area of Cu, SA Cu , i. e., the amount of Cu atoms per unit catalyst surface area is a key factor determining its catalytic activity of the copper‐based catalyst . The SA Cu of IS x C increases proportionally with the increasing Zn content up to 32 % (Table ).…”

Section: Resultsmentioning

confidence: 99%

“…Our study strongly supports the fact that methanol synthesis rate is proportional to the Cu surface area. The larger the effective surface area of Cu, i. e., greater number of Cu atoms per unit catalyst surface area results in greater contact with the reactant molecules during the same reaction time resulting in high catalytic activity . This suggests that the key factor for preparing a highly active catalyst for methanol synthesis is to have a high effective surface area of Cu in the catalyst.…”

Section: Resultsmentioning

confidence: 99%

“…With increase in Zn substitution from 0 % to 50 %, the specific surface area was increased gradually from 20.2 m 2 /g for IS0 C to 45.7 m 2 /g for IS50 C. It is well known that the effective surface area of Cu, SA Cu , i. e., the amount of Cu atoms per unit catalyst surface area is a key factor determining its catalytic activity of the copperbased catalyst. [31][32][33][34][35] The SA Cu of ISxC increases proportionally with the increasing Zn content up to 32 % ( Table 1). The increase in the Zn substitution implies that Zn replaces Cu to uniformly disperse CuO in the catalyst after calcination eventually resulting in decrease in particle size and increase in the specific surface area of Cu.…”

Section: Structure and Properties Of Cuo/zno Catalyst Prepared By Calmentioning

confidence: 99%

“…The larger the effective surface area of Cu, i. e., greater number of Cu atoms per unit catalyst surface area results in greater contact with the reactant molecules during the same reaction time resulting in high catalytic activity. [31][32][33] This suggests that the key factor for preparing a highly active catalyst for methanol synthesis is to have a high effective surface area of Cu in the catalyst. Hence, for the CuO/ZnO catalyst prepared by the IS method, it is necessary to have Zn/(Cu + Zn) ratio above 30 % to ensure high activity.…”

Section: Structure and Properties Of Cuo/zno Catalyst Prepared By Calmentioning

confidence: 99%

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Oriented Isomorphous Substitution: An Efficient and Alternative Route to Fabricate the Zn Rich Phase Pure (Cu_1−x,Zn_x)₂(OH)₂CO₃ Precursor Catalyst for Methanol Synthesis

et al. 2020

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A new methodology has been demonstrated for the synthesis of a series of phase pure (Cu1−x,Znx)2(OH)2CO3 precursors by isomorphous substitution of Zn2+ in the malachite structure. By following the present protocol, it was possible to synthesize the pure phase (Cu1−x,Znx)2(OH)2CO3 with substitution level as high as x=0.5, which is better than the maximum possible value achieved by coprecipitation method, i. e. x=0.31. The isomorphous substitution by Zn2+ leads to the change in the morphology of malachite crystals from flake‐like to regular needle‐like shape with high Zn dispersion. The activity of the calcined catalysts was increased by ∼1.5–1.7 fold for the hydrogenation of syngas to methanol as compared with those prepared from the traditional coprecipitation route. The synergy between Cu and ZnO was further demonstrated quantitatively by characterization of the catalysts treated with syngas at 250 °C.

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Heterogeneously Catalyzed CO ₂ Hydrogenation to Alcohols

Phongprueksathat

Urakawa

2021

CO2 Hydrogenation Catalysis

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Enhanced activity, selectivity and stability of a CuO-ZnO-ZrO2 catalyst by adding graphene oxide for CO2 hydrogenation to methanol

Cited by 141 publications

References 42 publications

Time evolution of the CO2 hydrogenation to fuels over Cu-Zr-SBA-15 catalysts

Time evolution of the CO2 hydrogenation to fuels over Cu-Zr-SBA-15 catalysts

Oriented Isomorphous Substitution: An Efficient and Alternative Route to Fabricate the Zn Rich Phase Pure (Cu_1−x,Zn_x)₂(OH)₂CO₃ Precursor Catalyst for Methanol Synthesis

Heterogeneously Catalyzed CO ₂ Hydrogenation to Alcohols

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Enhanced activity, selectivity and stability of a CuO-ZnO-ZrO2 catalyst by adding graphene oxide for CO2 hydrogenation to methanol

Cited by 141 publications

References 42 publications

Time evolution of the CO2 hydrogenation to fuels over Cu-Zr-SBA-15 catalysts

Time evolution of the CO2 hydrogenation to fuels over Cu-Zr-SBA-15 catalysts

Oriented Isomorphous Substitution: An Efficient and Alternative Route to Fabricate the Zn Rich Phase Pure (Cu1−x,Znx)2(OH)2CO3 Precursor Catalyst for Methanol Synthesis

Heterogeneously Catalyzed CO 2 Hydrogenation to Alcohols

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Product

Resources

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Oriented Isomorphous Substitution: An Efficient and Alternative Route to Fabricate the Zn Rich Phase Pure (Cu_1−x,Zn_x)₂(OH)₂CO₃ Precursor Catalyst for Methanol Synthesis

Heterogeneously Catalyzed CO ₂ Hydrogenation to Alcohols