Cu-Ga3+-doped wurtzite ZnO interface as driving force for enhanced methanol production in co-precipitated Cu/ZnO/Ga2O3 catalysts

Cored, Jorge; Lopes, Christian Wittee; Liu, Lichen; Soriano, José Manuel Gómez; Agostini, Giovanni; Solsona, Benjamín; Sánchez-Tovar, Rita; Concepción, Patricia

doi:10.1016/j.jcat.2022.01.032

Cited by 25 publications

(12 citation statements)

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“…Various catalysts based on CuZn-, In-, or PdZn-oxides have been developed and applied for the direct CO 2 hydrogenation to methanol. The achievements related to catalyst development and understanding of the reaction mechanisms and kinetics have been analyzed in plentiful review articles. ,,, CuZn-based catalysts modified with various promoters, e.g., In, − Pd, , Ga, Al, − Mg–Al, Zr, − and Ce, − were tested at relatively low temperatures (<523 K) and with stoichiometric H 2 /CO 2 = 3 feeds. A ternary Cu–Zn–ZrO 2 material shows promising performance due to its lower hydrophilicity and abundant oxygen vacancies in the lattice of ZrO 2 . − These properties affect the methanol selectivity and the CO 2 activation.…”

Section: Introductionmentioning

confidence: 99%

“…The achievements related to catalyst development and understanding of the reaction mechanisms and kinetics have been analyzed in plentiful review articles. 4,5,11,12 CuZn-based catalysts modified with various promoters, e.g., In, 13−15 Pd, 16,17 Ga, 18 Al, 19−21 Mg−Al, 22 Zr, 23−26 and Ce, 27−29 were tested at relatively low temperatures (<523 K) and with stoichiometric H 2 /CO 2 = 3 feeds. A ternary Cu−Zn−ZrO 2 material shows promising performance due to its lower hydrophilicity and abundant oxygen vacancies in the lattice of ZrO 2 .…”

Section: Introductionmentioning

confidence: 99%

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Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

et al. 2023

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Carbon dioxide (CO 2 ) capture and valorization have great potential for mitigating emissions of this greenhouse gas and accordingly for preserving the environment for future generations. In this regard, hydrogenation of CO 2 to methanol is highly attractive because this product is a valuable energy carrier and can also be used for production of various everyday commodities. Although many research papers on this topic have been published in the past decades, there is still a lack of fundamentals relevant to control catalyst performance. Herein, we demonstrate how statistically validated Big-Data analysis of available literature data identified hidden descriptors that can be applied for purposeful catalyst development and for identification of optimal reaction conditions. In view of catalyst development, the kinds of structural promoters or supports for bulk or supported Cu-, In-, or Pd-based catalysts are the most important descriptors for methanol selectivity, with Ce and Zr being the most efficient promoters. The type and the parameters of the preparation methods as well as the kind of active component precursors are also important in this regard. To validate the conclusion about the structural promoter, a series of supported CuZn-containing catalysts were prepared. The best-performing CuZn/CeO 2 catalyst outperformed the state-of-the-art CuZn-based catalysts tested at a total pressure of up to 30 bar using a feed with the ratio of H 2 /CO 2 of 3. In addition to the catalyst composition and the preparation method, our analysis suggests that the most often used Cu-based catalysts lose their methanol selectivity due to the decomposition of this product to CO. Our control experiments with the developed CuZn-based catalysts proved that this undesired reaction can be hindered when the catalyst support contains Ce or through increasing H 2 partial pressure. This knowledge is important for further catalyst development.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

et al. 2023

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“…Cu- − or In-containing − catalysts are typically applied for the CO 2 hydrogenation to CH 3 OH. The ongoing research in this field is focused on improving catalyst activity and/or the selectivity to CH 3 OH through designing materials possessing certainly structured CuO x or InO x species with different promoters. − There are only a few studies reporting CH 3 OH selectivity above 80% at CO 2 conversion above 5%.…”

Section: Introductionmentioning

confidence: 99%

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

et al. 2022

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CO2 hydrogenation to methanol (CH3OH) is widely accepted to proceed through two parallel reactions: (i) CH3OH formation and (ii) the reverse water gas shift (RWGS) reaction to CO. The latter reaction causes the loss of CH3OH selectivity. Our spatially resolved analysis of rates of product formation over a classical CuZnAlO x catalyst in a broad range of CO2 conversion degrees (from 0 to 90% of equilibrium conversion) suggests revisiting this concept. In comparison with the RWGS reaction, CH3OH decomposition to CO mainly contributes to the loss of CH3OH selectivity with a rising degree of CO2 conversion. Separate CH3OH decomposition tests in a broad range of experimental conditions proved that this side reaction is accelerated by H2O but negatively affected by H2 and rising total pressure. Moreover, the decomposition should occur on other sites rather than those participating in CH3OH synthesis from CO2 and can be practically suppressed above certain partial pressures of CH3OH and H2O due to site saturation. The sites responsible for the hydrogenation of CO2 to CH3OH, however, are not saturated. Thus, this product can be further produced in downstream catalyst layers. As this concept is valid for several CuZn-based catalysts, we provide fundamentals for the design of selective CH3OH synthesis catalysts and for optimizing reaction conditions. Operating under conditions, where the undesired CH3OH decomposition reaction is hindered, enabled us to achieve 93% CH3OH selectivity at 19% CO2 conversion (55% equilibrium conversion) at 50 bar and 200 °C using a feed with the ratio of H2/CO2 of 3.

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“…We can note that 2CuGaZrO x showed the top-rank catalytic performance (8.3% CO 2 conversion, 87% methanol selectivity, and 13% CO selectivity at 300 °C) for the CO 2 hydrogenation to methanol, compared with the Cu-based catalysts and solid solution catalysts in the literature (Table S6). ,,,− ,,,− As the Cu loading increased (5CuGaZrO x , 10CuGaZrO x ), the methanol selectivity dropped dramatically. This indicates that isolated single-atom Cu species preferred to promote the selective conversion of CO 2 to methanol, while the Cu clusters/nanoparticles played an essential role in the RWGS reaction. , The impregnated sample (2Cu/GaZrO x ) with surface Cu species in nanoscale size exhibited a lower methanol selectivity than the solid solution catalyst (2CuGaZrO x ) at high temperatures (>260 °C) under similar conversions (Figure S12), confirming the high catalytic selectivity of isolated single-atom Cu species in methanol synthesis.…”

Section: Resultsmentioning

confidence: 99%

Synergetic Interaction between Single-Atom Cu and Ga₂O₃ Enhances CO₂ Hydrogenation to Methanol over CuGaZrO_x

Han,

Xiao,

et al. 2023

ACS Catal.

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A Cu-based catalyst has prospects for practical use in selective hydrogenation of CO 2 to methanol. But the catalyst's structural complexity renders the elucidation of the nature of active sites a challenge. This work reports CuGaZrO x solid solutions with tunable Cu size scales and synergetic interactions between active sites for methanol synthesis. Atomically dispersed Cu species (Cu 1 −O 3 ) adjacent to the Zr site contribute to enhanced capacity for CO 2 adsorption/activation, and Ga sites are primarily responsible for H 2 dissociation over the CuGaZrO x solid solution with isolated Cu species. Further experimental and density functional theory (DFT) calculations reveal that the synergy between Cu and Ga species favors the hydrogenation of CO 2 to form CH 3 OH via a formate pathway while suppressing undesired CO production. This work provides insight into the active site structure and mechanistic pathway over a CuGaZrO x solid solution and efficient catalyst design for CO 2 hydrogenation to methanol.

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Cu-Ga3+-doped wurtzite ZnO interface as driving force for enhanced methanol production in co-precipitated Cu/ZnO/Ga2O3 catalysts

Cited by 25 publications

References 60 publications

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

Synergetic Interaction between Single-Atom Cu and Ga₂O₃ Enhances CO₂ Hydrogenation to Methanol over CuGaZrO_x

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Cu-Ga3+-doped wurtzite ZnO interface as driving force for enhanced methanol production in co-precipitated Cu/ZnO/Ga2O3 catalysts

Cited by 25 publications

References 60 publications

Identifying Catalyst Property Descriptors for CO2 Hydrogenation to Methanol via Big-Data Analysis

Identifying Catalyst Property Descriptors for CO2 Hydrogenation to Methanol via Big-Data Analysis

Revealing Origins of Methanol Selectivity Loss in CO2 Hydrogenation over CuZn-Containing Catalysts

Synergetic Interaction between Single-Atom Cu and Ga2O3 Enhances CO2 Hydrogenation to Methanol over CuGaZrOx

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Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Identifying Catalyst Property Descriptors for CO₂ Hydrogenation to Methanol via Big-Data Analysis

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

Synergetic Interaction between Single-Atom Cu and Ga₂O₃ Enhances CO₂ Hydrogenation to Methanol over CuGaZrO_x