Using CoCu2_2Ga/SiO2_2 to identify stability-issues in ethanol-selective Co-Cu alloyed catalysts in carbon monoxide hydrogenation

Hydrogenation of CO to higher alcohols such as ethanol is an attractive pathway for industrial production while avoiding competition with food crops. However, thermocatalytic ethanol production from syngas is currently hindered by the lack of selective catalysts. The structural integrity of ternary-alloyed CoCu2Ga nanoparticles supported on silica was studied during thermo-catalytic CO hydrogenation. Catalysts of four different CoCu$_2$Ga weight-loadings were tested catalytically under differential conversion, showing their different intrinsic selectivity during CO hydrogenation towards ethanol, methanol, and hydrocarbons. CoCu$_2$Ga catalysts with 3.5 wt% and 17.8 wt% proved most and least selective towards ethanol formation, respectively. These two were studied in depth using STEM-EDX of fresh and spent samples showing different size distributions of the nanoparticles for all samples, and a change in the Co/Cu distribution of the nanoparticles from fresh to spent samples. In situ characterization using XRD, XANES, and EXAFS during CO hydrogenation supported the findings of the STEM-EDX and elucidated that the fresh more homogenous catalyst consisting of ternary CoCu$_2$Ga nanoparticles de-alloyed into Cu-rich and CoGa-rich nanoparticles. This de-alloying was possibly driven by two factors: the metastable phase of CoCu$_2$Ga decreasing its free energy by separating Cu and Co; and the strong interaction between Co and CO further driving a segregation. From a theoretical standpoint, Cu-Co intermetallics present the most selective catalyst to form ethanol over methane and methanol. The experimental findings presented here support the theory, although further efforts are needed to improve structural stability during the catalytic reaction

A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In2O3/Al2O3 Catalysts for CO2 Hydrogenation

CO2 hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In2O3 (Palldium on Indium Oxide) catalysts show high CO2 conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal-efficient Pd/In2O3 species dispersed on Al2O3 can match the performance of pure Pd/In2O3 systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X-ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism

A high pressure operando spectroscopy examination of bimetal interactions in ‘Metal Efficient’ palladium/In 2 O 3 /Al 2 O 3 catalysts for CO 2 hydrogenation

CO2 hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In2O3 (Palldium on Indium Oxide) catalysts show high CO2 conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal‐efficient Pd/In2O3 species dispersed on Al2O3 can match the performance of pure Pd/In2O3 systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X‐ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism

Using CoCu₂Ga/SiO₂ to identify stability-issues in ethanol-selective Co-Cu alloyed catalysts in carbon monoxide hydrogenation

Hydrogenation of CO to higher alcohols such as ethanol is an attractive pathway for industrial production while avoiding competition with food crops. However, thermocatalytic ethanol production from syngas is currently hindered by the lack of selective catalysts. The structural integrity of ternary-alloyed CoCu2Ga nanoparticles supported on silica was studied during thermo-catalytic CO hydrogenation. Catalysts of four different CoCu2Ga weight-loadings were tested catalytically under differential conversion, showing their different intrinsic selectivity during CO hydrogenation towards ethanol, methanol, and hydrocarbons. CoCu2Ga catalysts with 3.5 wt% and 17.8 wt% proved most and least selective towards ethanol formation, respectively. These two were studied in depth using STEM-EDX of fresh and spent samples showing different size distributions of the nanoparticles for all samples, and a change in the Co/Cu distribution of the nanoparticles from fresh to spent samples. In situ characterization using XRD, XANES, and EXAFS during CO hydrogenation supported the findings of the STEM-EDX and elucidated that the fresh more homogenous catalyst consisting of ternary CoCu2Ga nanoparticles de-alloyed into Cu-rich and CoGa-rich nanoparticles. This de-alloying was possibly driven by two factors: the metastable phase of CoCu2Ga decreasing its free energy by separating Cu and Co; and the strong interaction between Co and CO further driving a segregation. From a theoretical standpoint, Cu-Co intermetallics present the most selective catalyst to form ethanol over methane and methanol. The experimental findings presented here support the theory, although further efforts are needed to improve structural stability during the catalytic reaction.</p

A High Pressure <i>Operando </i>Spectroscopy Examination of Bimetal Interactions in ‘Metal Efficient’ Palladium/In₂O₃/Al₂O₃ Catalysts for CO₂ Hydrogenation

CO2 hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In2O3 (Palldium on Indium Oxide) catalysts show high CO2 conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd−In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal-efficient Pd/In2O3 species dispersed on Al2O3 can match the performance of pure Pd/In2O3 systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X-ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism.</p