Structure control on kinetics of copper reduction in Zr–containing mixed oxides during catalytic hydrogenation of carbon oxides to methanol

Bonura, Giuseppe; Khassin, A. A.; Yurieva, T. M.; Cannilla, C.; Frusteri, F.; Frusteri, Leone

doi:10.1016/j.cattod.2018.10.038

Cited by 13 publications

(15 citation statements)

References 53 publications

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“…Other liquid products, such as ethers, alcohols, and hydrocarbons can be formed in addition to methanol during CO 2 hydrogenation, making a highly selective catalyst essential. Currently available commercial CZA catalysts are frequently modified with promoters, such as Ga 2 O 3 , ZrO 2 , and Cr 2 O 3 , as well as alkaline metals such as Na, K, Ca, and Mg, 6,8,11,[63][64][65][66][67][68][69][70][71][72][73][74][75] to affect Cu dispersion, particle size, and mobility that ultimately determine selectivity and stability.…”

Section: Llmentioning

confidence: 99%

Alcohol Production from Carbon Dioxide: Methanol as a Fuel and Chemical Feedstock

Sarp¹,

Hernandez²,

Chen³

et al. 2021

Joule

109

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Section: Llmentioning

confidence: 99%

Alcohol Production from Carbon Dioxide: Methanol as a Fuel and Chemical Feedstock

Sarp¹,

Hernandez²,

Chen³

et al. 2021

Joule

109

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“…Therefore, appropriate adsorption amount and adsorption strength of CO 2 are beneficial for the production of methanol, which give a guideline for the design of highly effective and efficient catalysts. On this account, considerable attention was recently paid to hydrotalcite-like compounds (HT) as catalyst precursors, because the catalyst systems derived from hydrotalcite structures possess homogeneous dispersion of metal cations at an atomic level, high stability against sintering, high specific surface area, and strongly basic properties [18][19][20].In the present work, we inspected the catalytic behavior of CuZnAl catalysts as obtained from hydrotalcite-like structures in a CO 2 -to-MeOH hydrogenation reaction. Irrespective of the extent of crystallinity of the coprecipitated phase, the influence of the Cu:Zn:Al ratio on the formation of well-dispersed and active metal particles, generated after calcination and reduction, was addressed.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

Tailoring of Hydrotalcite-Derived Cu-Based Catalysts for CO2 Hydrogenation to Methanol

et al. 2019

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Ternary Cu x Zn y Al z catalysts were prepared using the hydrotalcite (HT) method. The influence of the atomic x:y:z ratio on the physico-chemical and catalytic properties under CO 2 hydrogenation conditions was probed. The characterization data of the investigated catalysts were obtained by XRF, XRD, BET, TPR, CO 2 -TPD, N 2 O chemisorption, SEM, and TEM techniques. In the "dried" catalyst, the typical structure of a hydrotalcite phase was observed. Although the calcination and subsequent reduction treatments determined a clear loss of the hydrotalcite structure, the pristine phase addressed the achievement of peculiar physico-chemical properties, also affecting the catalytic activity. Textural and surface effects induced by the zinc concentration conferred a very interesting catalyst performance, with a methanol space time yield (STY) higher than that of commercial systems operated under the same experimental conditions. The peculiar behavior of the hydrotalcite-like samples was related to a high dispersion of the active phase, with metallic copper sites homogeneously distributed among the oxide species, thereby ensuring a suitable activation of H 2 and CO 2 reactants for a superior methanol production.Catalysts 2019, 9, 1058 2 of 15 hydroxycarbonate precursors [8][9][10]. On this account, studies on binary Cu x Zn y preparations enabled a deep understanding of the more complex ternary (Cu/Zn/Al) systems. Therefore, in binary preparations, typical crystalline phases range from Cu-rich to Zn-rich compositions, including malachite Cu 2 (OH) 2 CO 3 , zincian malachite (Cu x Zn y ) 2 (OH) 2 CO 3 , aurichalcite (Cu x Zn y ) 5 -(OH) 6 (CO 3 ) 2 , and hydrozincite Zn 5 (OH) 6 (CO 3 ) 2 . In particular, zincian malachite is currently considered to be the optimum precursor for the methanol synthesis catalyst, which facilitates formation of a highly porous meso-structure [11]. Considering that the maximum amount of Zn which can be substituted into the malachite lattice is 27 at.%, the optimum Cu:Zn molar ratio is close to 2:1 [12]. Higher Zn contents are desirable to facilitate further dilution of the Cu component, thereby enhancing metal dispersion, although this can result in a lower crystallinity of the zincian malachite phase. The final thermal decomposition of the hydroxycarbonates leads the formation of an intimate mixture of oxides, while an in situ reduction step is required to obtain the active catalyst.Recent approaches to synthesize methanol via catalytic hydrogenation of CO 2 , as the key for an anthropogenic chemical carbon cycle along with the need to reduce the economic impact of the conventional high-pressure synthesis of methanol via syngas, now address the research efforts toward novel preparation methods suitable for obtaining catalytic systems characterized by high copper dispersion and surface basicity to enhance CO 2 adsorption [13][14][15], as the competitive reaction pathway of reverse water gas shift (RWGS) leads to a loss of methanol production [16,17]. Therefore, appropriate adsorption amount a...

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“…In conclusion, zirconia phase composition clearly has a dramatic effect on the catalytic behavior of the final material; however, actually, the effect cannot be rationalized or clearly explained. Despite Tetragonal ZrO 2 is the most frequently used, and it is often considered as the best choice in terms of acid properties and oxygen vacancies compared to the monoclinic ZrO 2 , but the results are not univocal [1,2,[9][10][11][12][13][14]. On the other hand, amorphous zirconia, in spite of a non-crystalline nature, has a higher surface area, thus leading in several cases to a catalyst showing superior performances, as shown especially in some recent works [2,4,5,15,16].…”

Section: Preparation and Properties Of Copper-zirconia Catalystsmentioning

confidence: 99%

Copper–Zirconia Catalysts: Powerful Multifunctional Catalytic Tools to Approach Sustainable Processes

Scotti¹,

Bossola²,

Zaccheria³

et al. 2020

Catalysts

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Copper–zirconia catalysts find many applications in different reactions owing to their unique surface properties and relatively easy manufacture. The so-called methanol economy, which includes the CO2 and CO valorization and the hydrogen production, and the emerging (bio)alcohol upgrading via dehydrogenative coupling reaction, are two critical fields for a truly sustainable development in which copper–zirconia has a relevant role. In this review, we provide a systematic view on the factors most impacting the catalytic activity and try to clarify some of the discrepancies that can be found in the literature. We will show that contrarily to the large number of studies focusing on the zirconia crystallographic phase, in the last years, it has turned out that the degree of surface hydroxylation and the copper–zirconia interphase are in fact the two mostly determining factors to be controlled to achieve high catalytic performances.

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Structure control on kinetics of copper reduction in Zr–containing mixed oxides during catalytic hydrogenation of carbon oxides to methanol

Cited by 13 publications

References 53 publications

Alcohol Production from Carbon Dioxide: Methanol as a Fuel and Chemical Feedstock

Alcohol Production from Carbon Dioxide: Methanol as a Fuel and Chemical Feedstock

Tailoring of Hydrotalcite-Derived Cu-Based Catalysts for CO2 Hydrogenation to Methanol

Copper–Zirconia Catalysts: Powerful Multifunctional Catalytic Tools to Approach Sustainable Processes

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