Intense photoluminescence from mixed solutions of C70 and palladium octaethylporphyrin: A supramolecular heavy atom effect

Unusually intense near-infrared (near-IR) photoluminescence has been observed from mixed solutions of C70 and palladium octaethylporphyrin (PdOEP). The novel emission has a spectrum similar to C70 phosphorescence and an intensity that is approximately 20 times greater than that of C70 fluorescence. The emitting species is identified as a noncovalently bound, short-lived triplet exciplex of C70 with PdOEP. The emission is essentially C70 phosphorescence intensified by spin-orbit coupling from the Pd atom in the nearby metalloporphyrin. This supramolecular heavy atom effect increases the C70 emissive quantum yield to approximately 1 x 10(-2) in degassed hexane solution at room temperature. The radiative rate constant is enhanced by a factor of 10(5), to approximately 7 x 10(4) s(-1), which is a value that exceeds the phosphorescence rate constant of PdOEP. Comparative studies in a rigid poly(methyl methacrylate) (PMMA) matrix show that the excited state of the static C70-PdOEP complex decays in approximately 150 ns. A Job's plot analysis shows that the complex has a 1:1 stoichiometry. It forms dynamically in solution and is relatively weakly bound, with an estimated equilibrium constant near 100 M(-1). Qualitatively similar supramolecular heavy atom effects were also observed for complexes of PdOEP with C60 and fullerene derivatives.     

Hydrogen storage properties of isocyanide-stabilized palladium nanoparticles

Monodispersed palladium nanoparticles protected with n-octyl isocyanide were prepared, and their hydrogen absorption behavior was evaluated. The formation of the nanoparticles has been confirmed by means of 1H NMR and elemental analysis. Fourier transform infrared (FT-IR) showed that three distinct bands (2156, 1964, and 1611 cm(-1)) assigned to mono-, double-, and triple-bridged isocyanide ligands on the palladium surface. The average diameter of the particles was estimated to be 2.1 +/- 0.7 nm from observation by transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) analysis revealed that the particles contained Pd(0) with little amounts of Pd(II) or Pd(IV), in sharp contrast to the thiol- or phosphine-stabilized palladium nanoparticles. The absorption and desorption of hydrogen were reversible, and the reactions were much faster for the nanoparticles than for the bulk palladium metal, whereas the storage capacity was almost the same, 0.6 wt %.     

C20 carbon clusters: fullerene-boat-sheet generation, mass selection, photoelectron characterization

Electron-impact ionization in a time-of-flight mass spectrometer of C(20)H(0-3)Br(14-12) probes-secured from C(20)H(20) dodecahedrane by a "brute-force" bromination protocol-provided bromine-free C(20)H(0-2(3)) anions in amounts that allowed the clean mass-separation of the hydrogen-free C(20) (-) ions and the photoelectron (PE) spectroscopic characterization as C(20) fullerene (electron affinity (EA)=2.25+/-0.03 eV, vibrational progressions of 730+/-70). The extremely strained C(20) fullerene ions surfaced as kinetically rather stable entities (lifetime of at least the total flight time of 0.4 ms); they only very sluggishly expel a C(2) unit. The HOMO and LUMO are suggested to be almost degenerate (DeltaE=0.27 eV). The assignment as a fullerene was corroborated by the PE characterization of the C(20) bowl (EA=2.17+/-0.03 eV, vibrational progression of 2060+/-50 cm(-1)) analogously generated from C(20)H(10) corannulene (C(20)H(1-3)Br(9-8) samples) and comparably stable. Highly resolved low-temperature PE spectra of the known C(20) ring (EA=2.49+/-0.03 eV, vibrational progressions 2022+/-45 and 455+/-30 cm(-1)), obtained from graphite, display an admixture of, most probably, a bicyclic isomer (EA=3.40+/-0.03 eV, vibrational progression 455+/-30 cm(-1)). The C(20) (+(-)) and C(20)H(2) (+(-)) cluster ions generated from polybrominated perylene (C(20)H(0-2)Br(12-10)) have (most probably) retained the planar perylene-type skeleton (sheet, EA=2.47+/-0.03 eV, vibrational progressions of 2089+/-30 and 492+/-30 cm(-1) and EA=2.18+/-0.03 eV, vibrational progressions of 2105+/-30 and 468+/-30 cm(-1)).     

Novel optical oxygen sensing material: metalloporphyrin dispersed in fluorinated poly(aryl ether ketone) films

A series of new fluorine-containing poly(aryl ether ketone)s (8F-PEKEK(Ar); Ar: 2-2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (6FBA), 2,2-bis(4-hydroxyphenyl)propane (BA), 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane (3,4^′-BA) or 9,9^′-bis(4-hydroxyphenyl)fluorine (HF)) are synthesized and applied to the matrix of optical oxygen sensing using phosphorescence quenching of metalloporphyrins, platinum and palladium octaethylporphyrin, (PtOEP and PdOEP) by oxygen. The phosphorescence intensity of PtOEP and PdOEP in 8F-PEKEK(Ar) films decreased with increase of oxygen concentration. The ratio I₀/I₁₀₀ is used as a sensitivity of the sensing film, where I₀ and I₁₀₀ represent the detected phosphorescence intensities from a film exposed to 100% argon and 100% oxygen, respectively. For PtOEP in 8F-PEKEK(Ar) film, I₀/I₁₀₀ values are more than 20.0 and large Stern-Volmer constants more than 0.19%⁻¹ are obtained compared with PtOEP in polystyrene film. For PdOEP in 8F-PEKEK(Ar) film, on the other hand, the large I₀/I₁₀₀ values more than 143 are obtained. However, the Stern-Volmer plots of PdOEP in 8F-PEKEK(Ar) films exhibit considerable linearity at lower oxygen concentration range between 0% and 20%. These results indicate that PtOEP and PdOEP films are useful optical oxygen sensor at the oxygen concentration range between 0% and 100% and between 0% and 20%, respectively. The response times of PtOEP and PdOEP dispersed in 8F-PEKEK(Ar) films are 5.6 and 3.0 s on going from argon to oxygen and 110.1 and 160.0 s from oxygen to argon, respectively.     

Preparation and characterization of 4-dimethylaminopyridine-stabilized palladium nanoparticles

4-Dimethylaminopyridine (DMAP)-stabilized palladium nanoparticles with a mean diameter of 3.4 +/- 0.5 nm are prepared from the aqueous phase reduction of Na2PdCl4 using NaBH4 in the presence of DMAP. TEM and UV-vis spectroscopy characterization of the nanoparticle dispersion shows no obvious change in the nanoparticles several months after preparation. 1H NMR spectroscopy of the nanoparticles shows that the nanoparticle dispersion also contains a boron/DMAP complex and two palladium/DMAP complexes. One of the palladium complexes crystallizes out of the dispersion and is identified as Pd(DMAP)4(OH)2 by X-ray crystallography. Following extensive analysis, it is believed that the palladium/DMAP complexes are formed following the oxidation of the palladium nanoparticles. The prepared nanoparticle dispersion promotes selective hydrogen/deuterium (H/D) exchange on the carbon atoms alpha to the endocyclic nitrogen atom on the DMAP-stabilizing ligands through reaction with D2O. This activity is attributed to the presence of the nanoparticles rather than to the presence of the oxidized palladium/DMAP complexes.     

Quinoline-2-aldehyde thiosemicarbazone (QAT) as spectrophotometric reagent for palladium and nickel

A procedure is described for the extractive spectrophotometric determination of nickel and palladium with quinoline-2-aldehyde thiosemicarbazone. At pH 7.5 nickel forms a 1:2 complex which is soluble in chloroform and has an absorption maximum at 460 nm. Palladium forms a 1:2 complex with maximum absorbance at 510 nm which can be extracted into MIBK from 1M HCl. Both complexes are stable and conform to Beer's law. The molar absorptivities for nickel and palladium are 1.58 x 10(4) and 2.6 x 10(3) 1.mole(-1). cm(-1) respectively. The proposed method is suitable for detection and determination of nickel and palladium in the presence of associated metal ions. The results of the analysis of synthetic mixtures and standard samples are reported.     

Determination of palladium in gasoline by neutron activation analysis and automated column extraction

Palladium in gasoline was determined by means of neutron activation analysis (NAA) and selective sorbent extraction. Unleaded gasoline consistent with DIN EN 228, RON 95 was irradiated at a thermal neutron flux of phith = 1.68 x 10(13)s(-1)cm(-2) and an epithermal neutron flux of 3.32 x 10(11)s(-1)cm(-2) for t(irr) = 12 h. The irradiated gasoline was digested with nitric acid and palladium was then separated as N,N-diethyl-N'-benzoylthiourea complex by an automated column pre-concentration procedure. The eluate of 50 microL was dried on a filter paper and the 88.03 keV photons resulting from the decay of 109Pd were detected in a low level HPGe spectrometer with an efficiency of 35.5%. Severe interferences with other matrix constituents, especially 82Br could be overcome and the detection limit for palladium was improved to 3.4 ng/L at a confidence level of 90%. Although the analytical procedure applied yielded the lowest detection limit for palladium obtained in gasoline up to now, no indications for the presence of palladium were found.     

Determination of palladium with thiocyanate and rhodamine b by a solvent-extraction method

Sensitive spectrophotometric and spectrofluorimetric procedures for the determination of palladium have been developed, based on solvent-extraction of the ion-pair formed between Rhodamine B and the anionic complex of Pd(II) with thiocyanate. With an organic to aqueous phase-volume ratio of 1:5, the molar absorptivity is 9.0 x 10(4) l.mole(-1).cm(-1) and the absorbance of the reagent blank is 0.026. Spectrophotometrically, palladium can be determined in the range 0.1-8.8 mug. Spectrofluorimetrically, it can be determined over the range 0.04-1.5 mug. The spectrophotometric procedure has been applied to the determination of palladium in dental alloys, organopalladium compounds and hydrogenation catalysts.     

Spectrophotometric determination of palladium after solid-liquid extraction with 1-(2-Pyridylazo)-2-naphthol at 90 degrees C

An effective spectrophotometric determination of palladium with 1-(2-pyridylazo)-2-naphthol (PAN) using molten naphthalene as a diluent has been studied. A green complex of palladium with PAN is formed at 90 degrees C. In the range of pH 1.5-7.5, the complex is quantitatively extracted into molten naphthalene. The organic phase is anhydrously dissolved in CHCl(3) to be determined spectrophotometrically at 678 nm against the reagent blank. Beer's law is obeyed over the concentration range of 0.5-10 ppm. The molar absorptivity and Sandell's sensitivity are 1.2 x 10(4) l mol(-1) cm(-1) and 0.0070 mg cm(-2), respectively. The optimum conditions for determination are obtained. The interferences of various ions are observed in detail. The method has been applied to the determination of palladium in synthetic samples.     

Spectrophotometric determination of palladium with 5,6-dimethyl-1,3-indanedione-2-oxime

A rapid, sensitive and selective method has been developed for the determination of palladium with 5,6-dimethyl-1,3-indanedione-2-oxime in acetate buffer (pH 5.5). Beer's law is obeyed over the range 0.15-4.17 mug/ml palladium(II). The molar absorptivity at 370 nm is 2.98 x 10(4) 1.mole(-1).cm(-1). The method has been applied for the determination of palladium in synthetic mixtures corresponding to PtIr and Oakay alloys. An interesting feature of the system is the abnormal shape of the Job and molar-ratio plots obtained.     

Upconversion-powered photoelectrochemistry

Upconversion photochemistry occurring between palladium(II) octaethylporphyrin (PdOEP, 1) and 9,10-diphenylanthracene (DPA, 2) in toluene successfully sensitizes nanostructured WO(3) photoanodes (E(g) = 2.7 eV) to sub-bandgap non-coherent green photons at low power density.     

Highly specific spectrophotometric method for palladium(II) determination with 3-(5'-tetrazolylazo)-2,6-Diaminotoluene in the presence of chlorides. Kinetic and equilibrium study of reactions

3-(5'-tetrazolylazo)-2,6-Diaminotoluene (TEADAT, H(3)L(2+)) forms stable 1:1 and 1:2 (metal:ligand) pink-red complexes (lambda(max) 506 and 536 nm) with palladium(II). The apparent molar absorptivity of 1:2 complex is 5.2 x 10(4) 1.mol(-1). cm(-1) at 536 nm. Equilibrium constants beta*(nl) for reactions PdCl(2-)(4) + nH(3)L(2+) right harpoon over left harpoonright harpoon over left harpoon PdCl(4-n) (H(2)L)(2n-2)(n) + n Cl(-) + n H(+) were determined: logbeta*(1) = 4.09 +/- 0.05, logbeta*(2) = 8.40 +/- 0.02, corresponding stability conditional constants of PdCl(3)(H(2)L) and PdCl(2)(H(2)L)(2+)(2) were log beta(1) = 19.03, log beta(2) = 26.74. The formation of complexes was rather slow but could be speeded up considerably by the catalytic effect of trace amounts of thiocyanate. Constant absorbance values were thus reached in 2-5 min. A rapid, sensitive and highly specific method for the determination of palladium(II) at pH 1.42 in 0.25M NACl has been worked out with a detection limit of 0.54 mug. Interference of precious and common metal ions have been studied and the method has been applied for the determination of palladium in Pd asbestos, oakay alloys and various catalysts and for the determination of palladium in precious metals.     

Absorptiometric determination of palladium with 2,3-quinoxalinedithiol

A method is described for the absorptiometric determination of palladium, in the range 0.1-2.5 ppm, with 2,3-quinoxalinedithiol (H(2)qdt) in aqueous ethanol. The reagent, S-2-(3-mercaptoquinoxalinyl) thiuronium chloride (mgt), is hydrotysed rapidly to (qdt)(2-) at pH 10. In the presence of zinc, (qdt)(2-) is stabilized by complex formation and reagent blanks are reduced almost to zero. An anionic 1:2 complex of palladium(II) and (qdt)(-2) is formed at pH 10, having maximum absorbance at 454 nm and Sandell sensitivity index of 0.0032 mug cm (2). The reaction is moderately selective; equivalent concentrations of platinum(IV), iridiuin(IV) and rhodium(III) can be tolerated but gold(III), copper(II) and a few other metals interfere. Suggestions are made for masking interferences. The method is characterized by good precision, with a relative standard deviation of 0.25% at the 1-ppm level.     

Synthesis of N-o-methylphenyl-N'-(sodium p-aminobenzene-sulfonate) thiourea and its chromogenic reaction with palladium(II).

A new chromogenic reagent, N-o-methylphenyl-N'-(sodium p-aminobenzenesulfonate)thiourea (MSAT), has been synthesized and characterized by elemental analysis, (1)H-NMR, FT-IR and UV-Vis spectra. Based on the absorption spectrum of the colored complex of MSAT with palladium(II), a novel spectrophotometric method for the determination of palladium has been developed. In a pH 4.0 - 5.5 HAc-NaAc buffer solution, palladium(II) reacted with MSAT to form a stable yellow water-soluble complex with an apparent molar absorptivity of epsilon = 2.04 x 10(5) L mol(-1) cm(-1) at the maximum absorption of 318.0 nm. Beer's law was obeyed in the concentration range of 1.2 - 11.8 microg per 25 mL for palladium(II) with a correlation coefficient of 0.9997. The probable interfering ions and their tolerable limits have also been investigated in detail. The proposed method is simple, rapid, and sensitive, and has been applied to the determination of palladium in anode mud and ore samples with satisfactory results.     

o-Hydroxyacetophenone thiosemicarbazone as a reagent for the rapid spectrophotometric determination of palladium

o-Hydroxyacetophenone thiosemicarbazone has been synthesized and employed as a new reagent for the spectrophotometric determination of palladium(II), which forms two complex species with it in aqueous dimethylformamide at pH 6.0, these having 1:1 and 1:2 metal-ligand ratios. The Job and molar-ratio plots have an unusual shape that is due to the stepwise conversion of the 1:1 complex into the 1:2 species. The molar absorptivity at 370 nm is 9 x 10(3) l.mole(-1).cm(-1). Beer's law is obeyed over the range 0.42-10.6 mug/ml palladium.     

钛基体中离子注入钯的电催化性能

钛基体在能量40keV下,离子注入1×10^1^6～1×10^1^8Pd^+/cm^2.在30%的KOH溶液中,研究了这些电极对氢和氧析出的电催化性能.结果表明, 离子注入电极的催化活性明显地优于未注入的钛基体,并随着离子注入剂量的增大,催化活性增大. 由极化测量求得有关动力学参数.这些数据表明,用高剂量钯离子注入的钛电极, 其电化学性能与钯电极相似.根据AES和XPS数据,讨论了注入电极表面的组成     

Gravimetric and spectrophotometric determination of palladium with 2-hydroxy-5-methylpropiophenone oxime

2-hydroxy-5-methylpropiophenone oxime (HMP) reacts with palladium in strongly acidic media to form a yellow water-insoluble complex. Palladium has been determined gravimetrically and interference by certain ions studied. The yellow complex is extractable into carbon tetrachloride in the pH range 1-4. The absorption maximum of the complex lies at 375 mmu, and Beer's law is obeyed in the range 0-15 ppm of palladium. The sensitivity is 0.22 mug Pd/cm(2) for log I(0)/I = 0.001. The effect of a number of foreign ions has been studied and several can be tolerated to an appreciable extent. The ratio of metal: ligand in the complex is 1:2.     

Synthesis of 5-(5-nitro-2-pyridylazo)-2,4-diaminotoluene and its application to spectrophotometric determination of microamounts of palladium

A new pyridylazo reagent, 5-(5-nitro-2-pyridylazo)-2,4-diaminotoluene (5-NO(2)-PADAT) has been synthesized, and found to be a good chromogenic reagent for palladium. In sulfuric acid, hydrochloric acid and perchloric acid palladium reacts with 5-NO(2)-PADAT to form a 1:1 chelate, exhibiting an absorption maximum at 592 nm. The apparent molar absorptivity is 1.25 x 10(5) l(-1) mol(-1) cm(-1). Beer's law was obeyed in the range 0-0.9 microg ml(-1) Pd. Relatively large amounts of co-existing elements, including all other noble metals, can be tolerated. The method is simple and rapid, with high sensitivity and good selectivity and was applied to the determination of palladium in some industrial samples with satisfactory results.     

Pressure-induced enhancements of luminescence intensities and lifetimes correlated with emitting-state distortions for thiocyanate and selenocyanate complexes of platinum(II) and palladium(II)

The luminescence properties of thiocyanate and selenocyanate platinum(II) and palladium(II) complexes show strong variations with temperature and pressure. The d-d luminescence band maxima for [Pt(SCN)(4)](PPh(4))(2) (1), [Pt(SCN)(4)](n-Bu(4)N)(2) (2), and [Pt(SeCN)(4)](n-Bu(4)N)(2) (4) complexes are centered at ca. 14500 cm(-1) whereas those of the [Pd(SCN)(4)](n-Bu(4)N)(2) (3) and [Pd(SeCN)(4)](n-Bu(4)N)(2) (5) complexes are approximately 2000 cm(-1) lower in energy. Low-temperature luminescence spectra from single-crystal samples have broad bands with highly resolved vibronic structure indicating large displacements of the emitting-state potential energy minimum along several metal-ligand normal coordinates. The largest displacements involve the totally symmetric (a(1g)) stretching modes with frequencies of 295 cm(-1) (1), 303 cm(-1) (2), 274 cm(-1) (3), 195 cm(-1) (4), and 185 cm(-1) (5). The lower frequencies of these dominant progression-forming modes for the selenocyanate complexes lead to luminescence bands that are narrower by ca. 500 cm(-1) (fwhm) than those observed from the thiocyanate complexes. Under external pressures, the room-temperature luminescence intensities and lifetimes show considerable enhancement at pressures up to 40 kbar. This effect is largest for the palladium(II) complexes with lifetimes increasing from approximately 350 ns at ambient pressure up to 62 micros at 30 kbar, an increase by more than 2 orders of magnitude. The platinum(II) complexes exhibit a significant, but noticeably lesser increase of luminescence lifetimes and intensities with increasing pressure. The temperature- and pressure-dependent luminescence decay behavior is rationalized using the emitting-state molecular geometry determined from the resolved low-temperature luminescence spectra combined with the strong-coupling limit of radiationless decay theory.     

Surfactant gel adsorption of platinum(II), (IV) and palladium(II) as chloro-complexes and kinetic separation of palladium from platinum using EDTA.

A micellar solution of cetylpyridinium chloride (CPC) can separate into two phases due to a temperature change or to the addition of salts. Platinum(II), (IV) and palladium(II) reacted with chloride ions to form stable anionic complexes of PtCl4(2-), PtCl6(2-) and PdCl4(2-), respectively, and were adsorbed onto the CPC gel phase. The CPC phase plays the role of an ion-exchange adsorbent for the anionic complexes. By such a procedure, the precious metals of platinum and palladium could be separated from base metals such as copper, zinc and iron. The kinetic separation was performed by a ligand exchange reaction of the palladium(II) chloro-complex with EDTA at 60 degrees C. The anionic palladium(II)-EDTA complex could not bind the opposite charged CP+ and was desorbed from the CPC phase. In the aqueous phase, the recovery of palladium(II) by the double-desorption was 101.1 +/- 1.2%. The platinum(II) and (IV) chloro-complexes were stable for at least 30 min and remained in the CPC phase.