Size effect on deuterium behavior in nano-sized vanadium layers

Huang, Wen; Brischetto, Martin; Hjörvarsson, Bjørgvin

doi:10.1007/s11433-018-9381-8

Cited by 2 publications

(4 citation statements)

References 25 publications

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“…[ 43 ] Here we report on a dead layer near to the surface, which may also be explained by a decreased H–H interaction as suggested for nano‐sized vanadium systems. [ 44,45 ]…”

Section: Resultsmentioning

confidence: 99%

“…[43] Here we report on a dead layer near to the surface, which may also be explained by a decreased H-H interaction as suggested for nano-sized vanadium systems. [44,45] Both results, the localization of hydrogen and its thermodynamic properties (pcT) indicate that a bulk property is the rate limiting property of a surface process. Interestingly, already Ward et al had difficulties in assigning the activation energy of desorption limited permeation in Pd E des to a thermodynamic property: [4] the activation energy of desorption limited permeation (in thin Pd membranes) is higher than that in diffusion limited kinetics (Equation ( 12)), but with 40 to 50 kJ (2mol H) −1 much too weak to be associated to chemisorbed hydrogen (ΔH chemis ≃ −100 kJ (mol H 2 ) −1 [4,41] ).…”

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confidence: 99%

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Bulk Thermodynamics Determines Surface Hydrogen Concentration in Membranes

Billeter

Kazaz

Borgschulte

2022

Adv Materials Inter

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nonconverted reactants. In this step, hydrogen may be separated from the mixture, and reused in the reaction. In a future scenario with hydrogen as a main energy carrier, the separation and/or purification of the energetically costly hydrogen will become even more important. [1][2][3] A promising way is the use of hydrogen selective membranes made of hydrogen absorbing metals, such as Pd and its alloys. [4,5] The permeability of such membranes is determined by the surface properties of both sides (dissociation/recombination) and by the bulk permeability (diffusion and solubility). [4] There has been substantial research effort in finding cheaper materials with a higher permeability than that of Pd (e.g., V, Nb, Ta, and their alloys [6][7][8][9][10] ), however, expensive Pd and Pd based alloys remain the superior membrane materials owing to their favorable surface properties. [5,11] Cheap materials such as V-based alloys will revolutionize the technology, if their surface properties can be modified to match those of Pd. Despite this rather straightforward goal, there is a knowledge gap of what these desirable surface properties are. Most works refer to concepts from surface science which describe the physisorption, dissociation (barrier), and chemisorption of hydrogen. [12] However, additional steps-the hopping to subsurface sites and adjacent bulk sites-are needed to model the permeation process adequately. Nevertheless, due to the complex interaction of steps, the predictive power of modeling is limited [4,6,13] and-more importantly-experimental verification only possible by comparison with very basic experiments (permeation kinetics, e.g. ref.[14]) due to the lack of operando hydrogen analysis.Baldi et al. have demonstrated electron energy loss spectroscopy as an analysis method for bulk hydrogen in nano-particles. [15] In this paper, we further developed the method to be able to probe the surface hydrogen content of hydride thin films in situ by reflecting electron energy loss spectroscopy (REELS). The method is applied in an experimental approach, in which the surface properties of membranes can be intentionally modified and their hydrogen content determined under operating conditions. We demonstrate the existence of a rate-limiting step by direct observation of the dependence of the permeation on the hydrogen content in a Pd/V composite membrane. The modeling yields the relevance of the individual layers, making it possible to link the results to the ones obtained from hydrogen uptakeThe functioning of hydrogen selective metal membranes relies on the finetuned interaction of their surfaces with the inner bulk. The link between hydrogen permeation and surface concentration is unveiled using a novel combination of thin film preparation and surface science analysis to probe and intentionally modify the surface properties of palladium vanadium composite membranes. The in situ preparation allows for observation of ultraclean hydrogenation and the quantification of the permeation as a function of temperature and p...

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“…[ 43 ] Here we report on a dead layer near to the surface, which may also be explained by a decreased H–H interaction as suggested for nano‐sized vanadium systems. [ 44,45 ]…”

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Bulk Thermodynamics Determines Surface Hydrogen Concentration in Membranes

Billeter

Kazaz

Borgschulte

2022

Adv Materials Inter

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“…Hydrogen is one of the most technologically important energy carriers [4]. Its storage is significant and has been extensively investigated in vanadium-based alloys [5,6]. Recently, it was found that the vanadium hydrides in the superlattices systems show a profound finite-size effect on the thermodynamic properties at only a few monolayers and has attracted people's great attention [5,6].…”

Section: Introductionmentioning

confidence: 99%

“…Its storage is significant and has been extensively investigated in vanadium-based alloys [5,6]. Recently, it was found that the vanadium hydrides in the superlattices systems show a profound finite-size effect on the thermodynamic properties at only a few monolayers and has attracted people's great attention [5,6]. The physical origin of the effect is argued to be the missing hydrogen neighbors in the interface of vanadium [7].…”

Section: Introductionmentioning

confidence: 99%

Combined Light and Electron Scattering for Exploring Proximity Effects on Hydrogen Absorption in Vanadium

et al. 2021

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We investigate proximity effects on hydrogen absorption in ultra-thin vanadium layers through combing light transmission and electron scattering. We compare the thermodynamic properties of the vanadium layers, which are based on the superlattice structure of Cr/V (001) and Fe/V (001). We find an influence of the proximity effects on the finite-size scaling of the critical temperatures, which can be explained by a variation of dead layers in the vanadium. In addition to this, the proximity effects on hydrogen absorption are also verified from the changes of excess resistivity.

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Size effect on deuterium behavior in nano-sized vanadium layers

Cited by 2 publications

References 25 publications

Bulk Thermodynamics Determines Surface Hydrogen Concentration in Membranes

Bulk Thermodynamics Determines Surface Hydrogen Concentration in Membranes

Combined Light and Electron Scattering for Exploring Proximity Effects on Hydrogen Absorption in Vanadium

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