Unraveling the regulation of Mn in Cu-ZnOx formation during methanol synthesis from syngas over Cu/ZnO/Al2O3-Mn catalysts

Zhang, Zhenzhou; Cheng, Sifan; Liu, Wenqi; Chen, Baojian; Xin-hua, Gao; Gao, Jian; Tan, Yisheng; Dang, Shanshan; Tu, Weifeng

doi:10.1016/j.apcatb.2023.122985

Cited by 12 publications

(5 citation statements)

References 60 publications

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“…Next, the temperature-programmed desorption of CO (CO-TPD) was carried out to identify the types of surface sites for CO adsorption on Cu/MgO. Figure 8c shows three broad peaks in the temperature range 300−650 K, corresponding to weak (350−450 K), medium (450−600 K), and strong (550− 650 K) adsorption of CO. 32,51 The intensity of CO desorption at the medium temperature range significantly increased with an increase in the MgO content in Cu/MgO catalysts, it is similar to the trend of the intensity of the CO stretching vibration bands at 2085 cm −1 from CO−DRIFTS results, and thus the CO desorption at medium temperature ranges (450− 600 K) may refer to the CO adsorbed on Cu−MgO interface sites.…”

Section: Structure−performance Relationship For Co Hydrogenation On C...supporting

confidence: 69%

Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH₃OH

Liu,

Dang,

Cheng

et al. 2024

ACS Catal.

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In this work, the structure−performance relationship of Cu/MgO catalysts was established to unravel the role of MgO and the active sites for CO hydrogenation to CH 3 OH synthesis, by intrinsic kinetics, chemical titration, and a series of in situ (operando) spectroscopic characterizations. The turnover rates of CH 3 OH formation on Cu/MgO catalysts, especially when the Mg/(Mg + Cu) atomic ratio is 0.67, were significantly higher than that on monometallic Cu particles. We have demonstrated that the rates were insensitive to the particle size of Cu but depended linearly on the quantity of Cu−MgO interfacial sites. The interaction between Cu and MgO particles improved the dispersion of Cu particles and formed more highly active Cu−MgO interfacial sites as identified by precise characterization. Moreover, this study has also unraveled that both the HCO* and HCOO* species are predominantly reactive intermediates, and their sequential hydrogenation occurs concurrently for CH 3 OH formation over Cu/MgO catalysts during the CO−H 2 reaction.

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Section: Structure−performance Relationship For Co Hydrogenation On C...supporting

confidence: 69%

Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH₃OH

Liu,

Dang,

Cheng

et al. 2024

ACS Catal.

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“…The peak appearance at 993.3 and 996.7 eV are indexed to the metallic Zn, and the two peak at 987.7 and 990.6 eV are attributed to Zn 2+ in Zn/ZnO. Benefiting from the introduction of Au, the peak moved in the direction of lower kinetic energy clearly verifies the electron transfer from the Au to Zn [42–44] . To investigate the structure of the AuZn/ZnO in detail, X‐ray absorption fine structure (XAFS) analyses of Au L 3 ‐edge were performed without exposure to air atmosphere at room temperature.…”

Section: Resultsmentioning

confidence: 99%

“…Benefiting from the introduction of Au, the peak moved in the direction of lower kinetic energy clearly verifies the electron transfer from the Au to Zn. [42][43][44] To investigate the structure of the AuZn/ZnO in detail, X-ray absorption fine structure (XAFS) analyses of Au L 3 -edge were performed without exposure to air atmosphere at room temperature. The XANES spectra at the Au L 3 -edge of the AuZn/ZnO and Au foil are displayed (Figure 1e and Figure S8).…”

Section: Angewandte Chemiementioning

confidence: 99%

Selective CO₂‐to‐Syngas Conversion Enabled by Bimetallic Gold/Zinc Sites in Partially Reduced Gold/Zinc Oxide Arrays

Zhao,

Zhu,

Ouyang

et al. 2023

Angew Chem Int Ed

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Electrocatalytic CO2‐to‐syngas (gaseous mixture of CO and H2) is a promising way to curb excessive CO2 emission and the greenhouse gas effect. Herein, we present a bimetallic AuZn@ZnO (AuZn/ZnO) catalyst with high efficiency and durability for the electrocatalytic reduction of CO2 and H2O, which enables a high Faradaic efficiency (FE) of 66.4% for CO (corrected current density of 0.38 mA cm‐2) and 26.5% for H2 and a 3 h CO2‐to‐syngas at ‐0.9 V vs. the reversible hydrogen electrode (RHE). And the CO/H2 ratio shows a wide range from 0.25 to 2.50 over a narrow potential window (‐0.7 V to ‐1.1 V vs. RHE). In‐situ attenuated total reflection surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) combined with density functional theory (DFT) calculations reveals that the bimetallic synergistic effect between Au and Zn lower the activation energy barrier of CO2 molecules and facilitate electronic transfer, further highlight the potential to control the CO/H2 ratios for efficient syngas production using the coexisting Au sites and Zn sites.

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“…Mn-doping of CZA can result in enhanced methanol synthesis activity from CO/CO 2 /H 2 feeds. 541 The addition of Mn (2 mol % relative to Cu) affects the CZA formulation in two ways: it leads to a reduction in both Cu and ZnO particle sizes, and results in an increased degree of ZnO reduction under reaction conditions. The result of these effects is an increased number of Cu-ZnO x active sites, while the activation energy of the methanol synthesis reaction remained unchanged upon Mn addition, suggesting that the nature of the active sites is not affected by the promoter.…”

Section: Doping Strategiesmentioning

confidence: 99%

“…Mn-doping of CZA can result in enhanced methanol synthesis activity from CO/CO 2 /H 2 feeds . The addition of Mn (2 mol % relative to Cu) affects the CZA formulation in two ways: it leads to a reduction in both Cu and ZnO particle sizes, and results in an increased degree of ZnO reduction under reaction conditions.…”

Section: Doping Strategiesmentioning

confidence: 99%

The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts

Beck,

Newton,

van de Water

et al. 2024

Chem. Rev.

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The activity and durability of the Cu/ZnO/Al 2 O 3 (CZA) catalyst formulation for methanol synthesis from CO/CO 2 /H 2 feeds far exceed the sum of its individual components. As such, this ternary catalytic system is a prime example of synergy in catalysis, one that has been employed for the large scale commercial production of methanol since its inception in the mid 1960s with precious little alteration to its original formulation. Methanol is a key building block of the chemical industry. It is also an attractive energy storage molecule, which can also be produced from CO 2 and H 2 alone, making efficient use of sequestered CO 2 . As such, this somewhat unusual catalyst formulation has an enormous role to play in the modern chemical industry and the world of global economics, to which the correspondingly voluminous and ongoing research, which began in the 1920s, attests. Yet, despite this commercial success, and while research aimed at understanding how this formulation functions has continued throughout the decades, a comprehensive and universally agreed upon understanding of how this material achieves what it does has yet to be realized. After nigh on a century of research into CZA catalysts, the purpose of this Review is to appraise what has been achieved to date, and to show how, and how far, the field has evolved. To do so, this Review evaluates the research regarding this catalyst formulation in a chronological order and critically assesses the validity and novelty of various hypotheses and claims that have been made over the years. Ultimately, the Review attempts to derive a holistic summary of what the current body of literature tells us about the fundamental sources of the synergies at work within the CZA catalyst and, from this, suggest ways in which the field may yet be further advanced.

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Unraveling the regulation of Mn in Cu-ZnOx formation during methanol synthesis from syngas over Cu/ZnO/Al2O3-Mn catalysts

Cited by 12 publications

References 60 publications

Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH₃OH

Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH₃OH

Selective CO₂‐to‐Syngas Conversion Enabled by Bimetallic Gold/Zinc Sites in Partially Reduced Gold/Zinc Oxide Arrays

The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts

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Unraveling the regulation of Mn in Cu-ZnOx formation during methanol synthesis from syngas over Cu/ZnO/Al2O3-Mn catalysts

Cited by 12 publications

References 60 publications

Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH3OH

Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH3OH

Selective CO2‐to‐Syngas Conversion Enabled by Bimetallic Gold/Zinc Sites in Partially Reduced Gold/Zinc Oxide Arrays

The Enigma of Methanol Synthesis by Cu/ZnO/Al2O3-Based Catalysts

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Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH₃OH

Revealing the Interaction between Cu and MgO in Cu/MgO Catalysts for CO Hydrogenation to CH₃OH

Selective CO₂‐to‐Syngas Conversion Enabled by Bimetallic Gold/Zinc Sites in Partially Reduced Gold/Zinc Oxide Arrays

The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts