Formic acid (HCOOH) has great potential as an in situ source of hydrogen for fuel cells, because it offers high energy density, is non-toxic and can be safely handled in aqueous solution. So far, there has been a lack of solid catalysts that are sufficiently active and/or selective for hydrogen production from formic acid at room temperature. Here, we report that Ag nanoparticles coated with a thin layer of Pd atoms can significantly enhance the production of H₂ from formic acid at ambient temperature. Atom probe tomography confirmed that the nanoparticles have a core-shell configuration, with the shell containing between 1 and 10 layers of Pd atoms. The Pd shell contains terrace sites and is electronically promoted by the Ag core, leading to significantly enhanced catalytic properties. Our nanocatalysts could be used in the development of micro polymer electrolyte membrane fuel cells for portable devices and could also be applied in the promotion of other catalytic reactions under mild conditions.

The inelastic scattering of gas-phase OH radicals from a liquid hydrocarbon and a liquid perfluorinated polyether (PFPE) has been investigated. The surfaces examined were the potentially reactive, branched hydrocarbon squalane (C 30 H 62 , 2,6,10,15,19,23-hexamethyltetracosane) and the inert PFPE Krytox 1506 (F-[CF(CF 3 )-CF 2 O] 14ave -CF 2 CF 3 ). Superthermal OH was formed by 355-nm laser photolysis of a low pressure of HONO above the liquid surface. Laser-induced fluorescence (LIF) was used to determine the relative yields and nascent translational and rotational distributions of OH (V′ ) 0). The time-of-flight profiles from both liquids can be resolved, at least empirically, into two components. The dominant, faster component is consistent with direct, inelastic scattering. It has a higher average translational energy from PFPE than from squalane. This faster OH also has a higher Boltzmann-like rotational temperature for PFPE (655 ( 45 K) than for squalane (473 ( 27 K), in both cases considerably hotter than the incoming OH. For both liquids, there is also a slower component, with characteristics consistent with a thermalized, trapping-desorption mechanism. This is a higher proportion for squalane (0.22 ( 0.02) than for PFPE (0.09 ( 0.01). These results are consistent with squalane being the "softer" surface, exhibiting more efficient momentum transfer than PFPE, and more able to temporarily trap OH. Relative to PFPE, around half (0.49 ( 0.04) of the OH molecules that collide with squalane are lost, presumably due to reaction forming H 2 O. These results are compared with previous studies of the scattering of inert gas species from both squalane and PFPE. The reactive branching fraction of OH on squalane is discussed in the context of previous observations of enhanced reactivity at the gas-liquid interface.

The reactivity of photolytically generated, gas-phase, ground-state atomic oxygen, O((3)P), with the surfaces of a series of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([NTf(2)]) ionic liquids has been investigated. The liquids differ only in the length of the linear C(n)H(2n+1) alkyl side chain on the cation, with n = 2, 4, 5, 8, and 12. Laser-induced fluorescence was used to detect gas-phase OH v' = 0 radicals formed at the gas-liquid interface. The reactivity of the ionic liquids increases nonlinearly with n, in a way that cannot simply be explained by stoichiometry. We infer that the alkyl chains must be preferentially exposed at the interface to a degree that is dependent on chain length. A relatively sharp onset of surface segregation is apparent in the region of n = 4. The surface specificity of the method is confirmed through the nonthermal characteristics of both the translational and rotational distributions of the OH v' = 0. These reveal that the dynamics are dominated by a direct, impulsive scattering mechanism at the outer layers of the liquid. The OH v' = 0 yield is effectively independent of the bulk temperature of the longest-chain ionic liquid in the range 298-343 K, also consistent with a predominantly direct mechanism. These product attributes are broadly similar to those of the benchmark pure hydrocarbon liquid, squalane, but a more detailed analysis suggests that the interface may be microscopically smoother for the ionic liquids.

The relative reactivity of the liquid surface of a long-chain, partially branched hydrocarbon (squalane, C 30 H 62 ) with gas-phase O( 3 P) atoms has been measured as a function of liquid temperature. The O( 3 P) atoms were generated with a superthermal velocity distribution by 355 nm photolysis of NO 2 . Laser-induced fluorescence was used to detect the relative branching into specific OH product vibrational states. The yield of OH(V′)0) proves significantly less dependent on liquid surface temperature than the yield of OH(V′)1). Time-of-flight measurements of the escaping OH provide partially resolved product translational energy distributions. These profiles also differ between OH vibrational states. OH(V′)1) shows overall longer arrival times, but with a clear trend toward earlier times as the surface temperature is increased. OH(V′)0) shows little detectable variation of the distribution of arrival times over the range of temperatures investigated (263-333 K). We discuss the interpretation of these findings, taking account of earlier experimental work, which has indicated significant contributions from distinct "direct" and "trapping-desorption" reaction mechanisms, and new molecular dynamics simulations of the surface structure. There are a number of factors that may contribute, including both energetic and structural effects. It is not possible on the basis of the current evidence to discriminate conclusively between them. Nevertheless, we conclude, on balance, that structural effects may well be the more important. In particular, higher temperatures are predicted to promote more open structures. We speculate that this may enable more OH(V′)1) to escape before it is either vibrationally relaxed or, less probably, undergoes vibrationally enhanced reaction to produce H 2 O.

We have investigated the reactivity of photolytically generated ground-state, gas-phase atomic oxygen O(3P) with the surfaces of two related ionic liquids, 1-ethyl-3-methylimidazolium ([emim]) bis(trifluoromethyl-sulfonyl)imide ([NTf2]) and 1-dodecyl-3-methylimidazolium ([C12mim]) [NTf2]. The liquids differ only in the length of the alkyl side-chain on the cation. Laser-induced fluorescence was used to detect the gas-phase OH radicals formed at the gas−liquid interface. The considerable yield of OH from [C12mim][NTf2] in comparison to the undetectable amount from [emim][NTf2] cannot simply be explained by the difference in stoichiometry. We propose that this “chemical probe” method therefore provides strong evidence for the preferential accumulation of longer alkyl chains at the gas−liquid interface.

The inelastic scattering of OH radicals from the surfaces of a sequence of potentially reactive organic liquids: squalane (C(30)H(62), 2,6,10,15,19,23-hexamethyltetracosane); squalene (C(30)H(50), trans-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene); and oleic acid (C(18)H(34)O(2), cis-9-octadecanoic acid) was studied experimentally. A liquid long-chain perfluorinated polyether (PFPE, Krytox® 1506) was compared as a chemically inert reference. Gas-phase OH with an average laboratory-frame kinetic energy of 54 kJ mol(-1) was generated by 355-nm photolysis of a low-pressure of HONO a short distance (9 mm) above the liquid surface. Scattered OH was detected at the same distance by laser-induced fluorescence (LIF). Appearance profiles as a function of photolysis-probe delay were recorded for selected OH v' = 0, N' rotational levels. The efficiency of momentum transfer to the surface is least for PFPE and highest for squalane, with squalene and oleic acid intermediate, but in all cases the speed distributions are markedly too hot to be consistent with a thermal accommodation mechanism. The rotational distribution is found to be a function of scattered OH speed. The generally high rotational temperatures implied by the relative fluxes for N' = 1 and 5 were confirmed by LIF excitation spectra at the peak of the profile for each liquid. The trends in translational-to-rotational energy transfer were broadly consistent with the sequence in surface stiffness inferred from the translational inelasticity. The non-statistical distribution of OH fine-structure and Λ-doublet states produced by HONO photolysis appears to be effectively completely scrambled in collisions with the liquid surfaces. With due account taken of the product rotational distributions, and assuming that 100% of the OH scatters from PFPE, the integrated OH survival probabilities were: squalane (0.70 ± 0.08), squalene (0.61 ± 0.07) and oleic acid (0.76 ± 0.10). The 'missing' OH is presumed to have reacted at the liquid surface. Detailed comparison of the appearance profiles suggests that the main difference between squalane and squalene is loss of slower-moving OH, consistent with an additional capture mechanism at the vinyl sites.

This study examines clustering and hardening in W-2 at.% Re and W-1 at.% Re-1 at.% Os alloys induced by 2 MeV W + ion irradiation at 573 and 773 K. Such clusters are known precursors to the formation of embrittling precipitates, a potentially life-limiting phenomenon in the operation of fusion reactor components. Increases in hardness were studied using nanoindentation. The presence of osmium significantly increased postirradiation hardening. Atom probe tomography analysis revealed clustering in both alloys, with the size and number densities strongly dependent on alloy composition and irradiation temperature. The highest cluster number density was found in the ternary alloy irradiated at 773 K. In the ternary alloy, Os was found to cluster preferentially compared to Re. The implications of this result for the structural integrity of fusion reactor components are discussed. Crown

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