Cu–Zn Synergy for CO Hydrogenation to Ethanol and Methanol on CuZnO Catalysts

Gong, Jie; Liu, Jing; Yang, Denghui; Guo, Guangkai; Fan, Jinchuan; Huang, Wei

doi:10.1007/s10562-021-03776-5

Cited by 9 publications

(9 citation statements)

References 44 publications

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“…Furthermore, spectral analysis of Zn 2p and Zn LMM XAES was performed for the calcined and spent catalysts to further explore the interactions between Cu with ZnO and ZrO 2 at their interfaces. As shown in Figure e–h, Zn 2p spectra on the calcined catalysts (Figure e) display two peaks in the ranges of 1023.1–1024.2 and 1046.3–1047.3 eV, which are attributable to Zn 2p 3/2 and Zn 2p 1/2 of Zn 2+ species, respectively . When compared with the spent catalysts (Figure g), a slight negative shift of Zn 2p was observed, implying increased electron density on ZnO after hydrogenation.…”

Section: Results and Discussionmentioning

confidence: 99%

“…As shown in Figure 4e−h, Zn 2p spectra on the calcined catalysts (Figure 3e) display two peaks in the ranges of 1023.1−1024.2 and 1046.3−1047.3 eV, which are attributable to Zn 2p 3/2 and Zn 2p 1/2 of Zn 2+ species, respectively. 49 When compared with the spent catalysts (Figure 4g), a slight negative shift of Zn 2p was observed, implying increased electron density on ZnO after hydrogenation. It is worth noting that the binding energy of the Zn 2p core level of the CZZ-MSS was significantly lower than that of the ZZ-MSS in both the calcined catalyst and the spent catalyst, suggesting electron transfer from Cu to Zn at the Cu-ZnO x interfaces.…”

Section: Structural Textural and Compositional Properties Of Czz-mss ...mentioning

confidence: 94%

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Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO₂ Confined inside Mesoporous Silica Spheres for Enhancing CO₂ Hydrogenation to Methanol

Chen

Kosari

et al. 2023

ACS EST Eng.

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Achieving the desired catalytic activity and selectivity in CO2 hydrogenation to methanol remains a grand challenge using nonprecious metals. Herein, the well-known ternary Cu-ZnO-ZrO2 (CZZ) was spatially sequestered as fine, uniformly dispersed active interfaces onto an engineered mesoporous silica sphere (MSS), giving rise to Cu-ZnO-ZrO2/MSS (CZZ-MSS) with confined binary Cu-ZnO/Cu-ZrO2 and ternary interfaces that fostered methanol production under moderate conditions (30 bar and 200–280 °C). By systematically investigating the CZZ-MSS performance, we show that spatial confinement and optimization of the interfacial environment of the catalytically active interfaces inside well-fabricated mesoporous silica deliver a markedly enhanced specific methanol yield (2211 gMEOH·kgCu –1·h–1) compared to conventional supported catalysts including an industrial catalyst (368 gMEOH·kgCu –1·h–1) and a vast majority of reported catalysts. Besides, the strong metal–support interaction arising from interacting metallic Cu and metal oxides (ZnO and ZrO2) within the confined, ultrasmall nanoparticles (<3.0 nm) demotes the sintering of Cu NPs while retaining their H2 dissociation strength, resulting in superior and prolonged catalytic stability over 100 h. In situ DRIFTS of confined catalysts with monophasic, biphasic, and triphasic interfaces expectedly suggests the occurrence of different CO2 hydrogenation reaction paths over triphasic Cu-ZnO-ZrO2/MSS (formate pathway) compared to monophasic Cu/MSS (reverse water–gas shift (RWGS) pathway) and biphasic ZnO-ZrO2/MSS. From the appreciable insights gained herein, the rational support synthesis bringing the confinement effect to the robust ZnO-Cu-ZrO2 interface is the rationale behind the higher rate of methanol synthesis observed in the CO2 hydrogenation.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Structural Textural and Compositional Properties Of Czz-mss ...mentioning

confidence: 94%

Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO₂ Confined inside Mesoporous Silica Spheres for Enhancing CO₂ Hydrogenation to Methanol

Chen

Kosari

et al. 2023

ACS EST Eng.

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“…As can be seen from the figure, only the diffraction peak of Cu 0 was detected for Cu species, which was mainly due to the step-by-step reduction of Cu 2 + !Cu + !Cu 0 caused by partial decomposition of liquid paraffin during heat treatment. [15] In addition, there were no diffraction peaks of transition metal oxides (MnO, NiO and ZrO 2 ) due to their low content. [16] Compared with CZ, the diffraction peak intensity of Cu species in 2 %Ni-CZ is slightly enhanced and the intensity of in 2 %Mn-CZ and 2 %Zr-CZ is weakened.…”

Section: Crystal Structure and Textural Properties Of The Catalystsmentioning

confidence: 99%

Effects of Mn, Zr and Ni Promoters on the Performance of CuZnO Catalyst for Ethanol Synthesis via CO Hydrogenation

et al. 2022

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A series of CuZnO catalysts modified with Mn, Zr and Ni promoters were prepared by the complete liquid‐phase method. The performance of the modified catalysts for synthesis of ethanol from syngas was evaluated in slurry bed reactor. The results show that Mn and Zr can effectively improve the CO conversion and reduce the generation of hydrocarbons. Under the reaction conditions of 4 MPa and 280 °C, the ethanol selectivity reached 17.7 % in the 2 %Ni modified catalyst. The H2‐TPR characterization results showed that the presence of a large amount of highly dispersed Cu+ in the Mn and Zr‐promoted catalysts is conducive to the improvement of CO conversion. The XPS results showed that the addition of Ni was beneficial to the increase of surface oxygen vacancy content. It is speculated that the existence of oxygen vacancies is favorable to the insertion of CO molecules, and further conducive to the synthesis of ethanol.

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“…[5][6][7] The main disadvantage is their high cost. With respect to the synthesis of methanol, conventional CuZn catalysts are the most active, 8,9 but their selectivity to higher alcohols, except for isobutanol, does not exceed a few percent. Promising catalysts for the synthesis of higher alcohols are molybdenum-containing catalysts, which are very resistant to poisoning, including from sulphur.…”

Section: Introductionmentioning

confidence: 99%

LaCo_1−x−yCu_xTi_yO₃/KIT-6 perovskites: synthesis and catalytic behavior in syngas conversion to higher alcohols

et al. 2023

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Cu–Zn Synergy for CO Hydrogenation to Ethanol and Methanol on CuZnO Catalysts

Cited by 9 publications

References 44 publications

Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO₂ Confined inside Mesoporous Silica Spheres for Enhancing CO₂ Hydrogenation to Methanol

Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO₂ Confined inside Mesoporous Silica Spheres for Enhancing CO₂ Hydrogenation to Methanol

Effects of Mn, Zr and Ni Promoters on the Performance of CuZnO Catalyst for Ethanol Synthesis via CO Hydrogenation

LaCo_1−x−yCu_xTi_yO₃/KIT-6 perovskites: synthesis and catalytic behavior in syngas conversion to higher alcohols

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Cu–Zn Synergy for CO Hydrogenation to Ethanol and Methanol on CuZnO Catalysts

Cited by 9 publications

References 44 publications

Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO2 Confined inside Mesoporous Silica Spheres for Enhancing CO2 Hydrogenation to Methanol

Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO2 Confined inside Mesoporous Silica Spheres for Enhancing CO2 Hydrogenation to Methanol

Effects of Mn, Zr and Ni Promoters on the Performance of CuZnO Catalyst for Ethanol Synthesis via CO Hydrogenation

LaCo1−x−yCuxTiyO3/KIT-6 perovskites: synthesis and catalytic behavior in syngas conversion to higher alcohols

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Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO₂ Confined inside Mesoporous Silica Spheres for Enhancing CO₂ Hydrogenation to Methanol

Optimizing the Interfacial Environment of Triphasic ZnO-Cu-ZrO₂ Confined inside Mesoporous Silica Spheres for Enhancing CO₂ Hydrogenation to Methanol

LaCo_1−x−yCu_xTi_yO₃/KIT-6 perovskites: synthesis and catalytic behavior in syngas conversion to higher alcohols