S2p Binding Energies Research Articles

Roles of Polymerized Anionic Clusters Stimulating for Hydrolysis Deterioration in Li7P3S11

The atmospheric hydrolysis reaction in sulfide solid electrolytes (SEs) is destructive to their Li-ion conducting behavior, but a comprehensive understanding of their reaction steps is still lacking. Therefore, here, we studied the atmospheric deterioration of a well-known sulfide SE, Li7P3S11, based on the analogies between the hydrolysis and electrochemical reactions. Through analyzing the change in the S2p binding energy, we found that the anionic structures of both air-exposed and delithiated sulfides were altered owing to Li-ion loss. Considering the high diffusivity and massive hydrate formation ability of Li ions, we found that the anionic structures of both air-exposed and delithiated sulfides were altered. We showed that the hydrolysis of sulfide SEs with anionic polymerization has a thermodynamically favorable final state energy of −3.85 eV because S ions offer high degrees of freedom in their charge states ranging from −0.89 to −0.31e.

Atmospheric-pressure surface-diffusion dielectric-barrier discharge (SDDBD) plasma surface modification of PEDOT:PSS

Atmospheric-pressure surface-diffusion dielectric-barrier discharge (SDDBD) plasma is used to treat poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) inside a nitrogen-filled glove box. The SDDBD-treated PEDOT:PSS is then used as the hole transport layer of an inverted planar perovskite solar cell (PSC). Electrons and reactive ions in plasma can react with PEDOT:PSS. The resistivity of PEDOT:PSS decreases and then increases as SDDBD treatment time increases. This trend well corresponds to the PEDOT/PSS ratio, as indicated by the change of the X-ray photoelectron spectroscopy (XPS) S2p binding energy peak area ratio upon SDDBD treatment. Plasma treatment could eliminate part of excess PSS on the surface to uncover the PEDOT phase and change the PEDOT/PSS ratio, thereby altering the resistivity and work function of PEDOT:PSS. This influences the charge transport and charge extraction of PSCs, leading to a PSC with improved cell efficiency and reduced hysteresis. The best efficiency of PSC is achieved with 30-s SDDBD treatment.

XPS, single crystal X-ray diffraction and cyclic voltammetric studies on 1,10-phenanthroline and 2,2′-bipyridine adducts of bis(piperidinecarbodithioato- S, S′)cadmium(II) with CdS 4N 2 environment – A stereochemical and electronic distribution investigation

(1,10-Phenanthroline)bis(piperidinecarbodithioato- S, S ′)cadmium(II), [Cd(pipdtc) 2(1,10-phen)] ( 1) and (2,2′-bipyridine)bis(piperidinecarbodithioato- S, S′)cadmium(II), [Cd(pipdtc) 2(bipy)] ( 2) adducts were prepared and the crystal structures are reported. Cd–S and Cd–N distances and the angles subtended at cadmium are almost the same in both complexes but the Cd–S distances in the adducts are longer than those in Cd(pipdtc) 2 ( 3) complexes due to the presence of an additional neutral ligand. Thioureide C–N distance in 1 and 2 are supported by νC–N bands observed at 1471 and 1470 cm −1, respectively. S2p binding energies for the adducts show a significant reduction in value compared to the parent dithiocarbamate indicating the weakening of the Cd–S bond on adduct formation. The observed reduction in binding energy is due to the increased electron density on the metal in the adducts. The cyclic voltammetric study on the complexes also show an increase of electron density on cadmium in the adducts compared to Cd(pipdtc) 2.

H2S Gas Interaction with Pt(II)-Containing Polymetallaynes of Selected Chain Length: An XPS and EXAFS Study

The interaction between gaseous H2S and the surface of several metal-containing oligomers, investigated by emission and absorption spectroscopies, is presented and discussed. The polymetallayne trans-{Cl-[Pt(PBu3)2(CC-C6H4-C6H4-CC)]9Pt(PBu3)2Cl} and related model molecules, i.e. the binuclear transition metal dialkynyl bridged Pt(II) square planar complex trans, trans-[ClPt(PBu3)2(CC-C6H4-C6H4-CC)Pt(PBu3)2Cl], the tetranuclear linear oligomer trans-{Cl-[Pt(PBu3)2(CC-C6H4-C6H4-CC)]3Pt(PBu3)2Cl}, the tetranuclear cyclic oligomer cis-[Pt(PBu3)2(CC-C6H4-C6H4-CC)]4, were exposed to hydrogen sulfide and then investigated by X-ray photoelectron (XPS) and X-ray absorption (XAS) spectroscopies, in order to shed light on the gas/polymer interaction associated to the sensing properties of these materials. XPS measurements evidenced the presence of S in the polymetallayne samples exposed to H2S, and the measured S2p binding energy values correlate with H2S adsorbed by means of sulfur atoms chemically bonded to metal atoms, owing to the formation of sulfur-containing adducts. XAS data analysis suggested a square-pyramidal geometry around the transition metal with H2S in the apical position for the pentacoordinated platinum units.

Fabrication of MoO3 nanoparticles on an MoS2 template with (C4H9Li)xMoS2 exfoliation

Hexagonal MoO3 nanoparticles have been fabricated on an MoS2 template host via exfoliation of n-butyllithium-intercalated MoS2 powder in water. Their microstructures were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The Mo3d and S2p binding energies show that in the LiOH solution, some of the Mo atoms at the edges of the exfoliated MoS2 particles are oxidized to the +6 state and some of the S2− ligands are oxidized to SO42−. The TEM and XRD results confirm the existence of MoO3 nanoparticles and indicate that the aggregated MoO3 nanoparticles are distributed uniformly on the platelets of exfoliated MoS2 and have a diameter of about 5 nm. The process of exfoliation of n-butyllithium-intercalated MoS2 in water leads to formation of MoO3 and SO42−. The reaction procedure can be written as: MoS2 (exfoliation platelet) + O2 + OH− → MoO3 + SO42− +H2O.

Coloration and Chemical Bonding State of Sulfur in R2S-B2O3 (R=Li, Na, K) Glasses.

Simple binary alkali borate glasses containing sulfur were prepared by conventional melt quench method and chemical bonding states of sulfur were investigated by means of ultraviolet-visible (UV-VIS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and 11B MAS-NMR measurement. The glass samples were colored and colors changed with glass composition and alkali species. The blue coloration by absorption at around 585nm was explained with the formation of S3- anion spices. On the other hand, the glass samples colored in brown or red showed absorption spectrum around 450nm because of the formation of Sx2- anion (polysulfide ion) speices. S2p binding energy was around 161eV, and this values was lower than that of orthorhombic crystalline sulfur. From these results, it was suggested that sulfur was present with a negative charge in R2S-B2O3 glasses. In colored reddish brown regions, the formation of non-bridging oxygen from O1s spectrum in the glasses was noticed. Therefore, it is suggested that the formation of nonbridging oxygen in glasses largely effect the variation of sample coloration. The estimated fraction of fourcoordinated boron from 11B MAS-NMR measurment was nearly equal to oxide glass systems. As a result, it is assumed that the effect of sulfur on the conversion of boron coordinate number is small because of a low solubility of sulfur in this glass system.

Electron density distribution studies on ZnS 4N 2 chromophore in solution and solid phases: XPS and cyclic voltammetric studies on 1,10-phenanthroline and 2,2′-bipyridine adducts of bis(piperidinecarbodithioato-S,S′)zinc(II). Single crystal X-ray structure of (2,2′-bipyridine)bis-(piperidinecarbodithioato-S,S′)zinc(II)

(1,10-phenanthroline)bis(piperidinecarbodithioato-S,S′)zinc(II), [Zn(pipdtc) 2(1,10-phen)] ( 1) and (2,2′-bipyridine)bis(piperidinecarbodithioatao-S,S′)zinc(II), [Zn(pipdtc) 2(bipy)] ( 2) adducts were prepared and the crystal structure of 2 is reported. The Zn–S distances in 2 are longer than those in Zn(dtc) 2 complexes. The presence of an additional neutral ligand causes an increase of the Zn–S bond lengths. S2p binding energies show a significant reduction in value compared to the parent dithiocarbmate [Zn(pipdtc) 2]( 3), indicating the weakening of the Zn–S bond on adduct formation. The observed reduction in binding energy is due to the increased electron density on the metal in the adducts. The cyclic voltammetric study on the complexes also show an increase of electron density on zinc in the adducts compared to Zn(pipdtc) 2. The S–Zn–S angle in the adduct shows a reduction due to increased coordination around zinc. The thioureide C–N distance of 1.343(13) Å in compound 2 is in line with the νC–N observed at 1469 cm −1.

Chemical Bonding State of Sulfur in Na<sub>2</sub>S-SiO<sub>2</sub> Glasses

The structure and electronic states of Na2S-SiO2 oxysulfide glasses were investigated and the role of sulfur in the glasses is discussed. Na2S formed stable glass with SiO2 at an alkali concentration range similar to that of Na2O-SiO2 systems by the conventional melt-quench method. The obtained glasses were reddish brown in color and a remaining of sulfur was confirmed. X-ray photoelectron spectroscopy (XPS) was used to study the chemical bonding state of bridging and nonbridging anionic species in Na2S-SiO2 glass. The S2p binding energy of the glass was observed to be approximately 161eV. This value is lower than that of orthorhombic crystalline sulfur and almost the same as the value of Na2S. From the results, the electron density around sulfur was near to that of S2-. Furthermore, by 29Si magic angle spinning (MAS) and nuclear magnetic resonance (NMR) measurement, three clear-cut peaks were detected between 0 and -120ppm. It was assumed that a sulfur atom was joined to silicon via substitution for an oxygen atom, and was present as nonbridging sulfur in Na2S-SiO2 glass with low alkali ion concentration. On the other hand, it was revealed that a portion of the sulfur ions existed in an isolated state from the glass-network structure at high alkali content. The glass composition changed to a chemical composition that was more silica rich than predicted. The sulfur ions made sulfide clusters with the sodium ions isolated from the glass-network.

Chemical pattern on silica surface prepared by UV irradiation of 3-mercaptopropyltriethoxy silane layer: surface characterization and fibrinogen adsorption

A flat silica surface modified with 3-mercaptopropyltriethoxy silane (MTS) was patterned using UV irradiation and a custom-designed mask. The irradiated surface was characterized by X-ray photoelectron spectroscopy (XPS), scanning force microscopy (SFM) and water contact angle measurements. The XPS S2p spectra indicated that the UV treatment resulted in the oxidation of MTS sulfur. The optimal UV irradiation dose for patterning, estimated from the XPS S2p binding energy shifts and water contact angles of irradiated surfaces, was 4.8 J cm −2 at 270 nm. The surface patterns were visualized by total internal reflection fluorescence microscopy, while exposing the pattern to a solution of acridine orange, by water vapor condensation, and by SFM lateral force imaging in dilute electrolyte solution. The adhesion SFM measurements revealed the adhesion force only on the areas which were not UV-irradiated. The adsorption of fluorescein-labeled fibrinogen (FITC-Fgn) from dilute buffer solution also produced visual information on the pattern. The kinetics of FITC-Fgn adsorption onto the oxidized and unoxidized MTS-silica surfaces from dilute protein solution proceeded with identical initial adsorption rates. The steady-state FITC-Fgn adsorption was twice as large on the unoxidized MTS-silica than on the oxidized MTS-silica surface.

Extended fenske-hall calculation of inner-shell binding energies using ( Z + 1)-bazis sets: Sulfur-containing molecules

It is shown that the S1s and S2p binding energies and their chemical shifts in the molecules H 2S, SO 2, SF 6 and COS obtained with hole-state calculations using an extended Fenske-Hall method are in good agreement with experimental values if mixed ( Z + 1)-basis sets are applied.

The structure of 1,2‐dithioles studied by 13C n.m.r. spectroscopy

AbstractThe charge separation between the dithiole ring and oxygen in 3‐(1′,2′‐dithiole‐3′‐ylidene)‐6‐methyl‐2,3‐dihydropyran‐2,4‐diones and 3‐(1′,2′‐dithiole‐3′‐ylidene)‐2,3‐dihydrobenzo[b] pyran‐2,4‐diones has been determined by 13C and 19F n.m.r. spectroscopy. By both methods it is found that these compounds are relatively polar. A correlation is established between the 13C chemical shift of some carbon atoms and the S2p binding energies measured by e.s.c.a. in the 1,2‐dithiole derivatives. This correlation shows that these 13C shifts depend on the positive charge taken by the 1,2‐dithiole ring and can then constitute a convenient evaluation of this charge.