Size Dependent CO2 Reduction Activity of Ag Nanoparticle Electrocatalysts

Coinage metals (Au, Cu and Ag) are state-of-the-art electrocatalysts for the CO2 reduction reaction (CO2RR). Size-dependent CO2RR activity of Au and Cu has been studied, and increased H2 evolution reaction (HER) activity is expected for small catalyst particles with high population of undercoordinated corner sites. A similar consensus is still lacking for Ag catalysts because the ligands and stabilizers typically used to control particle synthesis can block specific active sites and mask inherent structure-property trends. This knowledge gap is problematic because increased performance and catalyst utilization are still needed to improve economic viability. We combined density functional theory, microkinetic modeling, and experiment to demonstrate a strong size-dependence for pristine Ag particles in the sub-10 nm range. Small diameter particles with a high population of Ag edge sites were predicted to favor HER, whereas CO2RR selectivity increased towards that of bulk Ag for larger diameter particles as the population of Ag(100) surface sites grew. Experimental results validated these predictions and we identified an optimal particle diameter of 8-10 nm that balanced selectivity and activity. Particles below this diameter suffered from poor selectivity, while larger particles demonstrated bulk-like activity and reduced catalyst utilization. These results demonstrate the size-dependent CO2RR activity of pristine Ag catalysts and will help guide future development efforts.

Effect of the Metal Deposition Order on Structural, Electronic and Catalytic Properties of TiO2-Supported Bimetallic Au-Ag Catalysts in 1-Octanol Selective Oxidation

Au and Ag were deposited on TiO2 modified with Ce, La, Fe or Mg in order to obtain bimetallic catalysts to be used for liquid-phase oxidation of 1-octanol. The effects of the deposition order of gold and silver, and the nature of the support modifying additives and redox pretreatments on the catalytic properties of the bimetallic Au-Ag catalysts were studied. Catalysts were characterized by low-temperature nitrogen adsorption–desorption, energy dispersive spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and ultraviolet-visible diffuse reflectance spectroscopy. It was found that pretreatments with hydrogen and oxygen at 300 °C significantly decreased the activity of AuAg catalysts (silver was deposited first) and had little effect on the catalytic properties of AgAu samples (gold was deposited first). The density functional theory method demonstrated that the adsorption energy of 1-octanol increased for all positively charged AuxAgyq (x + y = 10, with a charge of q = 0 or +1) clusters compared with the neutral counterparts. Lanthanum oxide was a very effective promoter for both monometallic and bimetallic gold and silver catalysts in the studied process.

Mechanistic Insights into CoOx–Ag/CeO2 Catalysts for the Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

Although Ag catalysts harbors potential for 5-hydroxymethylfurfural (HMF) oxidation to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), further oxidation into 2,5-furandicarboxylic acid (FDCA) remains a severe challenge. Herein, we propose a strategy to synthesize...