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Journal Articles

Selective adsorption of Pd(II) over Ag(I) in nitric acid solutions using nitrogen-donor-type adsorbents

Suzuki, Tomoya*; Otsubo, Ukyo*; Ogata, Takeshi*; Shiwaku, Hideaki; Kobayashi, Toru; Yaita, Tsuyoshi; Matsuoka, Mitsuaki*; Murayama, Norihiro*; Narita, Hirokazu*

Separation and Purification Technology, 308, p.122943_1 - 122943_7, 2023/03

 Times Cited Count:2 Percentile:22.61(Engineering, Chemical)

HNO$$_{3}$$ leaching is used in recycling Pd metal from spent products that primarily contain Ag, and most Pd residues are separated from solutions containing Ag(I). However, a small amount of Pd(II) often remains in these Ag(I) solutions. Therefore, the separation of Pd(II) and Ag(I) in HNO$$_{3}$$ solutions is essential to promote efficient Pd recycling. In this study, the separation of Pd(II) and Ag(I) in HNO$$_{3}$$ solutions was investigated using four N-donor-type adsorbents functionalized with amine (R-Amine), iminodiacetic acid (R-IDA), pyridine (R-Py), or bis-picolylamine (R-BPA). R-Amine, R-IDA, and R-Py selectively adsorbed Pd(II) over Ag(I), Cu(II), Ni(II), and Fe(III) from HNO$$_{3}$$ solutions (0.3-7 M), but R-Amine exhibited a lower Pd adsorption efficiency. In contrast, $$>$$90% of Pd(II), Ag(I), and Cu(II) were adsorbed by R-BPA over the entire range of HNO$$_{3}$$ concentrations. Structural analyses of the adsorbed metal ions using Fourier transform infrared spectroscopy and extended X-ray absorption fine structure spectroscopy revealed the separation mechanisms of the N-donor-type adsorbents. Pd(II) adsorption on R-IDA, R-Py, and R-BPA occurred via Pd(II) coordination of the functional groups (iminodiacetic acid, pyridine, and bis-picolylamine, respectively), whereas that on R-Amine occurred via anion exchange of NO$$_{3}$$$$^{-}$$ with [Pd(NO$$_{3}$$)$$_{4}$$]$$^{2-}$$. The coordinative adsorption mechanisms resulted in the higher Pd(II) adsorption behaviors of R-IDA, R-Py, and R-BPA. HCl (5.0 M) and thiourea (0.1 M) eluents desorbed 83% of Pd(II) from R-IDA and 95% from R-Py, respectively. R-Py was the most effective Pd(II) adsorbent based on adsorption selectivity and desorption efficiency.

Journal Articles

Characterization of F$$^{+}$$-irradiated graphite surfaces using photon-stimulated desorption spectroscopy

Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Nath, K. G.

Surface and Interface Analysis, 38(4), p.352 - 356, 2006/04

 Times Cited Count:3 Percentile:7.13(Chemistry, Physical)

We investigated the orientation nature at the top-most layers of F$$^{+}$$-irradiated graphite using polarization dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy which incorporates partial electron yield (PEY) detection and photon-stimulated ion desorption (PSID) techniques. The fluorine K-edge NEXAFS spectra conducted in PEY mode show no significant dependence on polarization angles. In contrast, NEXAFS spectra recorded in F$$^{+}$$ ion yield mode show enhanced yields at a feature of $$sim$$689.4 eV assigned as a $$sigma$$*(C-F) state relevant to =C-F sites, which depend on polarization angles. The C-F bonds prefer relatively tilting down the surface at the top-most layer, while the C-F bonds are randomly directed at deeper regions. We conclude that the difference in the orientation structures between the top surface and bulk is reflected in the NEXAFS recorded in the two different detection modes. It was also found that H$$^{+}$$- and F$$^{2+}$$- PSID NEXAFS spectra are helpful in understanding desorption mechanism, thus in analysing NEXAFS data.

Journal Articles

Mechanism of state-specific enhancement in photon-stimulated desorption as studied using a polarization-dependent technique

Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Wu, G.*; Kitajima, Yoshinori*

Surface Science, 593(1-3), p.310 - 317, 2005/11

 Times Cited Count:2 Percentile:11.64(Chemistry, Physical)

Using a newly developed rotatable time-of-flight mass spectrometer(R-TOF-MS) and polarized synchrotron radiation, orientation effect on fragmentation and desorption pathways occurring at the top-most layers of molecular solids have been investigated. Reported will be polarization-angle dependencies of TOF mass spectra, high-resolution electron- and ion-NEXAFS in condensed chlorobenzene.

Journal Articles

Direct and indirect processes in photon-stimulated ion desorption from condensed formamide

Ikeura, Hiromi*; Sekiguchi, Tetsuhiro; Baba, Yuji; Imamura, Motoyasu*; Matsubayashi, Nobuyuki*; Shimada, Hiromichi*

Surface Science, 593(1-3), p.303 - 309, 2005/11

 Times Cited Count:5 Percentile:26.1(Chemistry, Physical)

no abstracts in English

Journal Articles

Substitution effect on orientation of organosilicon compounds (CH$$_{3}$$)$$_{3}$$SiX (X = F, Cl, Br, I, NCO) as studied using NEXAFS spectroscopy

Sekiguchi, Tetsuhiro; Baba, Yuji; Shimoyama, Iwao; Nath, K. G.*; Uddin, M. N.*

Journal of Physics; Condensed Matter, 17(36), p.5453 - 5466, 2005/09

 Times Cited Count:1 Percentile:6.21(Physics, Condensed Matter)

The orientation nature of multilayer organosilicon compounds has been investigated by measuring the dependence of the Si K-shell near-edge X-ray absorption fine structures (NEXAFS) on the polarization angle. Two approaches helped to elucidate the orientation mechanism: the substitution effect and the deposition-rate dependence. The orientation angles of Si-X bond axes were obtained for trimethylsilyl halides, (CH$$_{3}$$)$$_{3}$$SiX (X =F Cl Br I NCO, condensed on Cu(111) at a low (82 K) temperature: the angles are 60, 73, 61, 55, and 55 degrees with respect to the surface normal, for X =F, Cl, Br, I, and NCO, respectively. Chloride (X =Cl) produces the most parallel tilt angle. The specific orientation nature of chloride is attributed to its strong dipole moment as well as the regular tetrahedron shape of the molecule. The molecular volumes calculated verify this view. Furthermore, deposition rates are found to greatly influence the growth manner: namely, high deposition rates led to a slightly perpendicular orientation of Si-X bond axis.

Journal Articles

Synchrotron radiation photoabsorption and photoemission spectroscopy for thermal-induced reoriented Si polymer

Nath, K. G.; Shimoyama, Iwao; Sekiguchi, Tetsuhiro; Baba, Yuji

Journal of Electron Spectroscopy and Related Phenomena, 144-147, p.323 - 326, 2005/06

 Times Cited Count:5 Percentile:27.33(Spectroscopy)

The effect of laser annealing on electronic atructures and molecular orientation for poly(dimethylsilane), {PDMS, [Si(CH$$_{3}$$)$$_{2}$$]$$_{n}$$} has been studied by synchrotron radiation photoemission and photoabsorption spectroscopy. Prior to annealing, PDMS powder was mounted on the basal plane of highly oriented pyrolytic graphite. Both Si 1s X-ray photoemission spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at Si 1s edge show that electronic structures have been modified due to annealing. Furthermore, the angle-dependent NEXAFS spectra clearly indicate that the annealed products maintain a specific orientation. Interestingly, no such kind of orientation is present in as-received PDMS powder as no angle-dependency is observed before annealing.

Journal Articles

Fragment-ion desorption from sulfur-containing amino acids by localized core-level excitation

Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao

Surface Review and Letters, 9(1), p.77 - 83, 2002/02

 Times Cited Count:4 Percentile:26.08(Chemistry, Physical)

no abstracts in English

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