Metal nanoparticles prepared by exsolution at the surface of perovskite oxides have been recently shown to enable new dimensions in catalysis and energy conversion and storage technologies owing to their socketed, well-anchored structure. Here we show that contrary to general belief, exsolved particles do not necessarily re-dissolve back into the underlying perovskite upon oxidation. Instead, they may remain pinned to their initial locations, allowing one to subject them to further chemical transformations to alter their composition, structure and functionality dramatically, while preserving their initial spatial arrangement. We refer to this concept as chemistry at a point and illustrate it by tracking individual nanoparticles throughout various chemical transformations. We demonstrate its remarkable practical utility by preparing a nanostructured earth abundant metal catalyst which rivals platinum on a weight basis over hundreds of hours of operation. Our concept enables the design of compositionally diverse confined oxide particles with superior stability and catalytic reactivity.

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Newcastle University ePrintsCumpson PJ, Portoles JF, Barlow AJ, Sano N. Accurate argon cluster-ion sputter yields: Measured yields and effect of the sputter threshold in practical depth-profiling by x-ray photoelectron spectroscopy and secondary ion mass spectrometry.Argon Gas Cluster-Ion Beam sources are likely to become widely used on x-ray photoelectron spectroscopy and secondary ion mass spectrometry instruments in the next few years. At typical energies used for sputter depth profiling the average argon atom in the cluster has a kinetic energy comparable with the sputter threshold, meaning that for the first time in practical surface analysis a quantitative model of sputter yields near threshold is needed. We develop a simple equation based on a very simple model. Though greatly simplified it is likely to have realistic limiting behaviour and can be made useful for estimating sputter yields by fitting its three parameters to experimental data. We measure argon cluster-ion sputter yield using a quartz crystal microbalance close to the sputter threshold, for silicon dioxide, poly(methyl methacrylate), and polystyrene and (along with data for gold from the existing literature) perform least-squares fits of our new sputter yield equation to this data. The equation performs well, with smaller residuals than for earlier empirical models, but more importantly it is very easy to use in the design and quantification of sputter depth-profiling experiments. V C 2013 AIP Publishing LLC.[http://dx.

Argon gas cluster ion beam sources are likely to become much more widely available on XPS and SIMS instruments in the next few years. Much attention has been devoted to their ability to depth profile organic materials with minimum damage. What has not been the focus of attention (possibly because it has been very difficult to measure) is the large ratio of sputter yield for organic materials compared with inorganic materials using these sources and the special opportunities this presents for studies of organic/inorganic interfaces. Traditional depth profiling by monatomic argon ions introduces significant damage into the organic overlayer, and because sputter rates in both organic and inorganic are similar for monatomic ions the interface is often ‘blurred’ due to knock‐on and other damage mechanisms. We have used a quartz crystal technique to measure the total sputter yield for argon cluster ions in a number of materials important in medical implants, biomaterials and diagnostic devices, including polymethyl methacrylate, collagen, hydroxyapatite, borosilicate glass, soda lime glass, silicon dioxide and the native oxides on titanium and stainless steel. These data fit a simple semi‐empirical equation very well, so that the total sputter yield can now be estimated for any of them for the entire range of cluster ion energy typical in XPS or SIMS. On the basis of our total sputter yield measurements, we discuss three useful ‘figures‐of‐merit’ for choosing the optimum cluster ion energy to use in depth profiling organic/inorganic samples. For highest selectivity in removing the organic but not the inorganic material the energy‐per‐atom in the cluster should be below 6 eV. A practical balance between selectivity and reasonably rapid depth profiling is achieved by choosing a cluster ion energy having between around 3 and 9 eV energy‐per‐atom. Copyright © 2013 John Wiley & Sons, Ltd.

We have previously reported that water addition (∼1000 ppm) to an N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C 3 mpyrFSI) superconcentrated ionic liquid electrolyte (50 mol % NaFSI) promoted the formation of a favorable solid electrolyte interphase (SEI) and resulted in enhanced cycling stability. This study reports the characterization of Na−metal anode surfaces cycled with these electrolytes containing different water concentrations (up to 5000 ppm). Morphological and spectroscopic characterization showed that water addition greatly influences the formation of the SEI and that ∼1000 ppm of water promoted the formation of an active and more uniform deposit, with larger quantities of SEI species (S, O, F, and N) present. Water addition to the electrolyte system is also proposed to promote the formation of a new complex between the FSI anions, water molecules, and sodium cations as components of the SEI. For both dry and wet (∼1000 ppm) electrolytes, the SEIs were mainly composed of NaF, metal oxide (i.e., Na 2 O), and the complex, suggested to be Na 2 [SO 3 -N-SO 2 F]•nH 2 O (n = 0−2). Postcycling SEM analysis of the Na−metal electrodes after extensive cycling (500 cycles, 1.0 mA•cm −2 , 1.0 mA•.cm −2 ) was used to estimate the minimal average cycling efficiency (ACE), which was enhanced by water addition: up to ∼99% for the 1000 ppm cell compared to ∼98% for the dry cell. Two distinct deposit morphologies, a microporous and a compact layer deposit, were evident after extended cycling in the wet and dry electrolytes. The presence of both the microporous and compact layer deposits on Na−metal surfaces cycled with the wet electrolyte, along with the distinct chemistry and morphology of the SEI, all contributed to a more stable symmetric cell voltage profile and lower cell polarization. In contrast, a higher fraction of microporous deposits and the absence of compact layer formation in the dry electrolyte were associated with higher cell polarization potentials and the occurrence of dendrites.

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