Density Functional Theory Analysis of Reaction Mechanism of Hypophosphite Ions on Metal Surfaces

Kunimoto, Masahiro; Shimada, Takuya; Odagiri, Shuichi; Nakai, Hiromi; Homma, Takayuki

doi:10.1149/1.3609000

Cited by 38 publications

(30 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Our previous study showed hydrogen atom of hypophosphite ion spontaneously dissociates to migrate and provides dissociative chemisorption of hypophosphite ion on Pd surface in the case of "via H". 9 However, because P-O bond is generally strong, the case of "via O" does not involve such dissociative chemisorption of hypophosphite ion. 25 To compare adsorption affinity in these cases equally, two bonds, P-H and P-O, were fixed so that the adsorption does not involve any dissociation.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Analysis of Adsorption Structure of Hydrated Hypophosphite Ion on Pd (111) Surface

et al. 2012

Self Cite

View full text Add to dashboard Cite

The influence of water molecules on the reaction behavior of hypophosphite ion, which acts as a reducing agent for electroless deposition, on metal surfaces was elucidated by calculating the adsorption structure of hydrated hypophosphite ion on a Pd surface using Monte-Carlo simulation and density functional theory calculations. Through geometrical optimization, the most favorable structure of the hydrated hypophosphite ion was obtained, in which six water molecules interact with the oxygen of hypophosphite ion and no water interacts with the hydrogen of hypophosphite ion. Further calculations indicated that the hydrated hypophosphite ion adsorbed on the Pd surface via hydrogen.

show abstract

Section: Resultsmentioning

confidence: 99%

Theoretical Analysis of Adsorption Structure of Hydrated Hypophosphite Ion on Pd (111) Surface

et al. 2012

Self Cite

View full text Add to dashboard Cite

show abstract

“…Adsorption energies of water molecule on Pd (111) and Cu (111) were calculated by Phatak et al to be ¹2.9 © 10, and ¹2.1 © 10 kJ/mol respectively. 26 Meanwhile, adsorption energies of hypophosphite on Pd (111) and Cu (111) were calculated in our previous study to be ¹84.09, and ¹49.36 kJ/mol respectively, 18 which are larger than those of water molecule. Therefore, water molecules thermodynamically have little influence on the adsorption of hypophosphite ion.…”

Section: Methodsmentioning

confidence: 96%

“…These elementary steps are (i) adsorption, (ii) dehydrogenation, and (iii) oxidation with hydroxyl group attack. 1921 In this previous study, we showed that the catalytic activities of metals on the hypophosphite ion reaction are primarily dependent on the dehydrogenation step; 18 dehydrogenation on metal surfaces with strong catalytic activity on the oxidation of hypophosphite, such as a Pd surface, must overcome only a small energy barrier to proceed, whereas dehydrogenation on surfaces with little catalytic activity, such as a Cu surface, is too destabilized to proceed. Our further analysis indicated that orbital interaction between hypophosphite and the metal surface in the adsorption step plays a critical role in initiating the dehydrogenation.…”

Section: Introductionmentioning

confidence: 99%

“…11,12 Several theoretical analyses of reaction mechanisms of reducing agents such as hypophosphite ions, 13 dimethylamine borane, 14 formaldehyde, 15 and others 16,17 have been carried out. In particular, our previous study 18 revealed the catalytic activity of metal surfaces in each elementary step of the hypophosphite ion reaction from a molecular level. These elementary steps are (i) adsorption, (ii) dehydrogenation, and (iii) oxidation with hydroxyl group attack.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical Analysis of Catalytic Activity of Metal Surfaces on Reaction of Hypophosphite Ion

2012

Self Cite

View full text Add to dashboard Cite

To elucidate the mechanism of catalytic activity of metal surfaces on the reaction of hypophosphite ions, which act as a reducing agent for electroless deposition, molecular orbital interactions between hypophosphite ions and metal surfaces were analyzed using density functional theory. Pd (111) and Cu (111) were chosen as the surfaces with high and low catalytic activity, respectively. The electronic states of adsorption systems were analyzed using the Mülliken population analysis. The position of the d-band plays a key role in determining the catalytic activity on P-H bond cleavage of hypophosphite. The Pd surface has a d-band near the Fermi level and contains a vacancy; this enables the donation and back-donation effect to occur on the adsorbed hypophosphite and promotes P-H bond cleavage. On the other hand, the Cu surface has a d-band in the deep energy area and contains no vacancy; the donation and back-donation effect is not induced and P-H bond cleavage is not promoted. This difference in the degree of promotion of P-H cleavage is responsible for the difference in the catalytic activity on P-H cleavage and dehydrogenation of hypophosphite ions, which in turn explains the difference in the catalytic activity during the entire hypophosphite oxidation process.

show abstract

“…1,2 However, the complexity of the reaction mechanism for reductant oxidation makes it difficult to improve the efficiency of electroless deposition. 3 In order to obtain fundamental knowledge about the reaction mechanism of oxidation of the reductants for more precise control of the solidliquid interface in this process, we have investigated the behavior of reductants absorbed on a Cu surface from experimental and computational points of view in this paper.…”

Section: Introductionmentioning

confidence: 99%

Raman and DFT Study of the Reaction of Hydrazine and Hypophosphite on a Cu Surface in the Electroless Deposition Process

et al. 2013

Self Cite

View full text Add to dashboard Cite

Oxidation of the reductants is a dominant factor in the electroless deposition process. In order to obtain fundamental knowledge about the reaction mechanism of reductant oxidation for more precise control of the solid-liquid interface in this process, we have attempted to characterize the behavior of reductants adsorbed on Cu surface by using plasmon antenna enhanced Raman scattering. The concentric-patterned antenna coated with Cu, which consisted of a dimple array with single hole or a single hole with coaxial dimples, was designed by Finite Difference Time Domain (FDTD) calculation to enhance the electric field by focusing surface plasmons. By using this antenna and comparing the spectra to the results of Density Functional Theory (DFT) calculations, Raman peaks of adsorbed reductants on Cu were identified. Furthermore, we examined the conformation of adsorbed reductants by DFT calculation of the adsorption model of reductants on fcc-Cu(111) surface. As a result, the nature of reductant adsorption on Cu surface has been investigated from a computational point of view and an experimental point of view, and such in-situ characterization will be useful for analysis of a variety of systems at solid-liquid interface.

show abstract

Density Functional Theory Analysis of Reaction Mechanism of Hypophosphite Ions on Metal Surfaces

Cited by 38 publications

References 19 publications

Theoretical Analysis of Adsorption Structure of Hydrated Hypophosphite Ion on Pd (111) Surface

Theoretical Analysis of Adsorption Structure of Hydrated Hypophosphite Ion on Pd (111) Surface

Theoretical Analysis of Catalytic Activity of Metal Surfaces on Reaction of Hypophosphite Ion

Raman and DFT Study of the Reaction of Hydrazine and Hypophosphite on a Cu Surface in the Electroless Deposition Process

Contact Info

Product

Resources

About