Quick on the uptake : Palladium nanoparticles were fabricated simply by immersing {[Zn3(ntb)2(EtOH)2]?4 EtOH}n ( 1 ) in an MeCN solution of Pd(NO3)2 at room temperature, without any extra reducing agent. 3 wt % PdNPs@[ 1 ]0.54+(NO3?)0.54 significantly increase H2 uptake capacities, both at 77 K and 1 bar and at 298 K and high pressures (see picture, red curve) compared to [Zn3(ntb)2]n (black). ntb=4,4′,4′′‐nitrilotrisbenzoate.
The hydrogen storage properties of metal nanoparticles change with particle size. For example, in a palladium–hydrogen system, the hydrogen solubility and equilibrium pressure for the formation of palladium hydride decrease with a decrease in the particle size, whereas hydrogen solubility in nanoparticles of platinum, in which hydrogen cannot be stored in the bulk state, increases. Systematic studies of hydrogen storage in Pd and Pt nanoparticles have clarified the origins of these nanosize effects. We found a novel hydrogen absorption site in the hetero‐interface that forms between the Pd core and Pt shell of the Pd/Pt core/shell‐type bimetallic nanoparticles. It is proposed that the potential formed in the hetero‐interface stabilizes hydrogen atoms rather than interstitials in the Pd core and Pt shells. These results suggest that metal nanoparticles a few nanometers in size can act as a new type of hydrogen storage medium. Based on knowledge of the nanosize effects, we discuss how hydrogen storage media can be designed for improvement of the conditions of hydrogen storage.相似文献
Three‐dimensional covalent organic frameworks (COFs) have been demonstrated as a new class of templates for nanoparticles. Photodecomposition of the [Pd(η3‐C3H5)(η5‐C5H5)]@COF‐102 inclusion compound (synthesized by a gas‐phase infiltration method) led to the formation of the Pd@COF‐102 hybrid material. Advanced electron microscopy techniques (including high‐angle annular dark‐field scanning transmission electron microscopy and electron tomography) along with other conventional characterization techniques unambiguously showed that highly monodisperse Pd nanoparticles ((2.4±0.5) nm) were evenly distributed inside the COF‐102 framework. The Pd@COF‐102 hybrid material is a rare example of a metal‐nanoparticle‐loaded porous crystalline material with a very narrow size distribution without any larger agglomerates even at high loadings (30 wt %). Two samples with moderate Pd content (3.5 and 9.5 wt %) were used to study the hydrogen storage properties of the metal‐decorated COF surface. The uptakes at room temperature from these samples were higher than those of similar systems such as Pd@metal–organic frameworks (MOFs). The studies show that the H2 capacities were enhanced by a factor of 2–3 through Pd impregnation on COF‐102 at room temperature and 20 bar. This remarkable enhancement is not just due to Pd hydride formation and can be mainly ascribed to hydrogenation of residual organic compounds, such as bicyclopentadiene. The significantly higher reversible hydrogen storage capacity that comes from decomposed products of the employed organometallic Pd precursor suggests that this discovery may be relevant to the discussion of the spillover phenomenon in metal/MOFs and related systems. 相似文献
In order to maximize the performance of nanocrystals in a specific application, it is necessary to control both their size and shape. Here we report a one-pot protocol that allows us to separate growth from nucleation for achieving better control over the size and shape of Pd nanocrystals. The two processes are temporally separated from each other, although the synthesis is carried out in the same reaction container. Size control is achieved by simply varying the ratio between the amounts of precursor allocated to the growth and nucleation processes. With the involvement of seeds at a fixed number, increasing the amount of precursor for growth leads to increasingly larger nanocrystals. Shape control is made possible by varying the capping agent, with bromide leading to a cubic shape and citrate inducing the formation of an octahedral shape. The synthesis can also be scaled up by at least tenfold without compromising the quality. 相似文献
