ABSTRACT
Single-atom catalysts are thought to be the pinnacle of catalysis. However, for many reactions, their suitability has yet to be unequivocally proven. Here, we demonstrate why single Pd atoms (PdSA) are not catalytically ideal for generating H2 from formic acid as a H2 carrier. We loaded PdSA on three silica substrates, mesoporous silicas functionalized with thiol, amine, and dithiocarbamate functional groups. The Pd catalytic activity on amino-functionalized silica (SiO2-NH2/PdSA) was far higher than that of the thiol-based catalysts (SiO2-S-PdSA and SiO2-NHCS2-PdSA), while the single-atom stability of SiO2-NH2/PdSA against aggregation after the first catalytic cycle was the weakest. In this case, Pd aggregation boosted the reaction yield. Our experiments and calculations demonstrate that PdSA in SiO2-NH2/PdSA loosely binds with amine groups. This leads to a limited charge transfer from Pd to the amine groups and causes high aggregability and catalytic activity. According to the density functional calculations, the loose binding between Pd and N causes most of Pd's 4d electrons in amino-functionalized SiO2 to remain close to the Fermi level and labile for catalysis. However, PdSA chemically binds to the thiol group, resulting in strong hybridization between Pd and S, pulling Pd's 4d states deeper into the conduction band and away from the Fermi level. Consequently, fewer 4d electrons were available for catalysis.
ABSTRACT
We explored the electrowetting behavior of a hydrofluoroester solvent, Novec 7100 (Novec), as a liquid droplet on a Au(111) electrode in water (0.05 M KClO4). Comparison with the electrowetting of hexadecane (HD) highlighted the significance of the lower adhesion energy and static friction energy of Novec than those of HD. The electrode potential-dependent contact angle θ of a Novec droplet showed little hysteresis. When potentials were set by means of potential steps, a Novec droplet increased its θ at more positive potentials than the potential of zero charge (pzc) of the Au(111) electrode. We found that the key factor of the electrowetting behavior for Novec is its low adhesion energy and static friction energy. The static friction energy of the oils to the Au(111) electrode surface was evaluated by a comparative analysis of the potential dependence of the interfacial tension at the solid/water interface, ΔγS/W-E curve, calculated from electrochemical surface charge data and the experimental cos θ-E curve: 2.6 mN/m for HD and 0.95 mN/m for Novec. When Br- was added in the aqueous solution to allow its adsorption on the Au surface surrounding a Novec droplet, the potential of maximum cos θ was shifted to negative. Overall, although the Novec droplet showed a narrower range of θ change than a HD droplet, the Novec droplet seldom got stuck to the surface as far as potential step was used, reflecting the narrower plateau region of θ near the pzc. Also, the specific adsorption of a coexistent anion was a significant factor of θ. This work has featured the significance of a slippy droplet on an electrode surface, giving an impact on the technology of microfluid transportation control by electric potentials.