A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales.
In order to disclose the dominant interfacial interaction between amino acids and ordered mesoporous materials, the adsorption behaviors of five amino acids on four mesoporous materials were investigated in aqueous solutions with adjustable amino acid concentration, ion strength, and pH. The selected amino acids were acidic amino acid glutamic acid (Glu), basic amino acid arginine (Arg), and neutral amino acids phenylalanine (Phe), leucine (Leu), and alanine (Ala), and the selected mesoporous materials were SBA-15, Al-SBA-15, CH3(10%)-SBA-15, and CH3(20%)-SBA-15. The adsorption capacities of Glu and Arg were strongly dependent on pH and surface charge of the mesoporous adsorbent. The adsorption of Phe showed pH insensitivity but depended on the surface organic functionalization of mesoporous adsorbent. On the basis of the theoretical analysis about the interaction between amino acid and adsorbent, such a remarkable difference was attributed to the different nature of the interaction between amino acid and adsorbent. Arg could be readily adsorbed on the surface of SBA-15, especially Al-SBA-15, under appropriate pH in which the electrostatic interaction was predominant. The driving force of Phe adsorption on mesoporous adsorbent mainly came from the hydrophobic interaction. Therefore, the adsorption capability of Arg decreased with increasing ion strength of solution, while the adsorption capability of Phe increased with the increasing degree of CH3 functionalization on SBA-15. For neutral amino acid Phe, Ala, and Leu, the adsorption capability increased with the increase of the length of their side chains, which was another evidence of hydrophobic effect. Thus, all the adsorption of amino acids on mesoporous silica materials can be decided by the combined influence of two fundamental interactions: electrostatic attraction and hydrophobic effect.
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