The diminished surface-area-normalized catalytic activity of highly dispersed Pt nanoparticles compared with bulk Pt is particularly intricate, and not yet understood. Here we report on the oxygen reduction reaction (ORR) activity of well-defined, size-selected Pt nanoclusters; a unique approach that allows precise control of both the cluster size and coverage, independently. Our investigations reveal that size-selected Pt nanoclusters can reach extraordinarily high ORR activities, especially in terms of mass-normalized activity, if deposited at high coverage on a glassy carbon substrate. It is observed that the Pt cluster coverage, and hence the interparticle distance, decisively influence the observed catalytic activity and that closely packed assemblies of Pt clusters approach the surface activity of bulk Pt. Our results open up new strategies for the design of catalyst materials that circumvent the detrimental dispersion effect, and may eventually allow the full electrocatalytic potential of Pt nanoclusters to be realized.

The metal organic framework material Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate) has been synthesized using different routes: under solvothermal conditions in an autoclave, under atmospheric pressure and reflux, and by electrochemical reaction. Although the compounds display similar structural properties as evident from the powder X-ray diffraction (XRD) patterns, they differ largely in specific surface area and total pore volume. Thermogravimetric and chemical analysis support the assumption that pore blocking due to trimesic acid and/or methyltributylammoniummethylsulfate (MTBS) which has been captured in the pore system during reaction is a major problem for the electrochemically synthesized samples. Isobutane and isobutene adsorption has been studied for all samples at different temperatures in order to check the potential of Cu3(BTC)2 for the separation of small hydrocarbons. While the isobutene adsorption isotherms are of type I according to the IUPAC classification, the shape of the isobutane isotherm is markedly different and closer to type V. Adsorption experiments at different temperatures show that a somewhat higher amount of isobutene is adsorbed as compared to isobutane. Nevertheless, the differential enthalpies of adsorption are only different by about 5 kJ/mol, indicating that a strong interaction between the copper centers and isobutene does not drive the observed differences in adsorption capacity. The calculated breakthrough curves of isobutene and isobutane reveal that a low pressure separation is preferred due to the peculiar shape of the isobutane adsorption isotherms. This has been confirmed by preliminary breakthrough experiments using an equimolar mixture of isobutane and isobutene.

The metal−organic framework (MOF) compound Cu3(BTC)2(H2O)3·xH2O (BTC = benzene 1,3,5-tricarboxylate) was prepared by solvothermal synthesis under ambient pressure and structurally characterized by powder X-ray diffraction and nitrogen adsorption at 77 K. X- and Q-band CW electron spin resonance and hyperfine sublevel correlation spectroscopies were used to explore the coordination state and location of the Cu(II) ions in the porous coordination polymer. Cupric ions were found to be present in two different chemical environments:  (a) Cu(II)2 clusters in the paddle-wheel building blocks of the Cu3(BTC)2 network, giving rise to an antiferromagnetically coupled spin state in accordance with previous susceptibility measurements (J. Appl. Phys. 2000, 87, 6007). However, the cross-linking of the paddle wheels by the BTC linker leads to an additional spin exchange among dimers as evidenced by the characteristics of the S = 1 ESR signal of their excited spin state. (b) In addition, paramagnetic monomer Cu(II) species are accommodated in the pore system of Cu3(BTC)2. They coordinate to adsorbed water molecules and form [Cu(H2O)6]2+ complexes, which are inhomogeneously distributed over the Cu3(BTC)2 pore system.

Colloidal platinum nanoparticles are obtained via a surfactant-free polyol process in alkaline ethylene glycol. In this popular synthesis, ethylene glycol functions as solvent and reducing agent. The preparation procedure is known for its reproducibility to obtain 1-2 nm nanoparticles, but at the same time the controlled preparation of larger nanoparticles is challenging. A reliable size control without the use of surfactants is a fundamental yet missing achievement for systematic investigations. In this work it is demonstrated how the molar ratio between NaOH and the platinum precursor determines the final particle size and how this knowledge can be used to prepare and study in a systematic way supported catalysts with defined size and Pt to carbon ratio. Using small-angle X-ray scattering, transmission electron microscopy, infrared spectroscopy, X-ray absorption spectroscopy, pair distribution function and electrochemical analysis it is shown that changing the NaOH/Pt molar ratio from 25 to 3, the Pt nanoparticle size is tuned from 1 to 5 nm. This size range is of interest for various catalytic applications, such as the oxygen reduction reaction (ORR). Supporting the nanoparticles onto a high surface area carbon, we demonstrate how the particle size effect can be studied keeping the Pt to carbon ratio constant, an important aspect that in previous studies could not be accomplished.