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<p>A hydrophobic surface modification strategy was developed to enhance the activity and durability of Cu/ZnO catalysts for CO<sub>2</sub> hydrogenation to methanol. Using stearic acid as a surface functionalization agent, Cu/ZnO catalysts were synthesized via oxalate-assisted solid–state grinding followed by controlled hydrophobic treatment. Systematic characterization (XRD, TEM, BET, and XPS) revealed that stearate modification suppressed particle agglomeration, yielding smaller Cu crystallites (≈ 25.6&#xa0;nm), increased surface area (≈62.1 m<sup>2</sup>&#xa0;g⁻<sup>1</sup>), and an optimized pore structure compared to the untreated catalyst. The resulting hydrophobic interface reduced water adsorption and mitigated surface oxidation, contributing to preserved catalytic functionality during CO<sub>2</sub> hydrogenation. The optimized Cu/ZnO–2&#xa0;mM catalyst exhibited superior catalytic performance, achieving a CO<sub>2</sub> conversion of 15.8 ± 0.5% and a methanol selectivity of 78.8% at 200&#xa0;°C, corresponding to a methanol space–time yield of 87.17&#xa0;g&#xa0;kg⁻<sup>1</sup>&#xa0;h⁻<sup>1</sup>, which is 26% higher than that of the untreated catalyst. Stability tests over 100&#xa0;h showed sustained catalytic performance without observable activity decay. While direct quantification of carbon deposition was not conducted, the stable methanol productivity and unchanged phase composition after reaction suggest limited deactivation under the investigated conditions. Density functional theory analysis provides qualitative insight into the relative stability of formate-related intermediates on Cu surfaces, suggesting that modified interfacial environments may influence the relative prevalence of methanol formation and reverse water–gas shift pathways under the investigated conditions, without assigning facet-specific mechanisms or definitive kinetic barriers. Overall, this structure-driven wettability engineering strategy highlights the role of surface microenvironment control in improving catalytic efficiency and durability, offering a practical approach for low-temperature CO₂-to-methanol conversion.</p>

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Hydrophobic microenvironment engineering regulates surface chemistry in Cu–Zn catalysts for CO2 hydrogenation

  • 期刊论文

  • 发表日期：

    2026年6月21日

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  • Z. Hamidzadeh,
  • A. S. Naeini

摘要

A hydrophobic surface modification strategy was developed to enhance the activity and durability of Cu/ZnO catalysts for CO2 hydrogenation to methanol. Using stearic acid as a surface functionalization agent, Cu/ZnO catalysts were synthesized via oxalate-assisted solid–state grinding followed by controlled hydrophobic treatment. Systematic characterization (XRD, TEM, BET, and XPS) revealed that stearate modification suppressed particle agglomeration, yielding smaller Cu crystallites (≈ 25.6 nm), increased surface area (≈62.1 m2 g⁻1), and an optimized pore structure compared to the untreated catalyst. The resulting hydrophobic interface reduced water adsorption and mitigated surface oxidation, contributing to preserved catalytic functionality during CO2 hydrogenation. The optimized Cu/ZnO–2 mM catalyst exhibited superior catalytic performance, achieving a CO2 conversion of 15.8 ± 0.5% and a methanol selectivity of 78.8% at 200 °C, corresponding to a methanol space–time yield of 87.17 g kg⁻1 h⁻1, which is 26% higher than that of the untreated catalyst. Stability tests over 100 h showed sustained catalytic performance without observable activity decay. While direct quantification of carbon deposition was not conducted, the stable methanol productivity and unchanged phase composition after reaction suggest limited deactivation under the investigated conditions. Density functional theory analysis provides qualitative insight into the relative stability of formate-related intermediates on Cu surfaces, suggesting that modified interfacial environments may influence the relative prevalence of methanol formation and reverse water–gas shift pathways under the investigated conditions, without assigning facet-specific mechanisms or definitive kinetic barriers. Overall, this structure-driven wettability engineering strategy highlights the role of surface microenvironment control in improving catalytic efficiency and durability, offering a practical approach for low-temperature CO₂-to-methanol conversion.