Coprecipitation of gold(III) complex ions with manganese(II) hydroxide and their stoichiometric reduction to atomic gold (Au(0)): analysis by Mössbauer spectroscopy and XPS

To elucidate the formation process of precursor of gold-supported manganese dioxide (MnO2), the coprecipitation behavior of [AuCl4-n(OH)n](-) (n=0-4) (Au(III)) complex ions with manganese(II) hydroxide (Mn(OH)2 and the change in their chemical state were examined. The Au(III) complex ions were rapidly and effectively coprecipitated with Mn(OH)(2) at pH 9. According to the M?ssbauer spectra for gold (Au) coprecipitated with Mn(OH)2, below an Au content of 60 wt% in the coprecipitates, all of the coprecipitated Au existed in the atomic state (Au(0)), while, above an Au content of 65 wt%, part of the gold existed in the Au(III) state, and the proportion increased with increasing coprecipitated Au content. Based on the results of X-ray photoelectron spectroscopy, Mn(II) in Mn(OH)2 converted to Mn(IV) in conjunction with coprecipitation of Au(III) complex ions. These results indicate that the rapid stoichiometric reduction of Au(III) to Au(0) is caused by electron transfer from Mn(II) in Mn(OH)2 to the Au(III) complex ion through an Mn-O-Au bond.     

Zeolite-supported gold nanoparticles for selective photooxidation of aromatic alcohols under visible-light irradiation

With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99?%) under visible-light irradiation at ambient temperature. Au/zeolite photocatalysts were characterised by UV/Vis, X-ray photoelectron spectroscopy (XPS), TEM, XRD, energy-dispersive spectroscopy (EDS), Brauner-Emmet-Teller (BET) analyses, IR and Raman techniques. The surface plasmon resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible-light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterisation data and the photocatalytic performances, we proposed a possible photooxidation mechanism.     

Measurements of 127I M?ssbauer spectra for iodine compounds

127I M?ssbauer spectra of good quality were obtained at 20 K using a Zn127mTe source produced by high flux neutron irradiation of 66Zn-126Te at reactor core. The M?ssbauer spectra for KI and some iodine(III) compounds with absorption intensity of about 5% suggest that the 127I M?ssbauer spectroscopy is useful in elucidating the bonding nature of the iodine compounds. Preparative method of the M?ssbauer source and experimental technique are reported in detail.     

Enhanced photocatalytic activity of ZnO nanoparticles by surface modification with KF using thermal shock method

ZnO nanoparticles were modified with KF using thermal shock method at various temperatures in order to improve the photocatalytic activity of ZnO under both UVA and visible light irradiation. The influences of KF-modification on the crystal structure, morphology, UV–visible absorption, specific surface area as well as surface structure of ZnO were respectively characterized by XRD, FE-SEM, UV–Visible diffuse reflectance, N₂ adsorption and XPS spectroscopy. The photocatalytic activity was evaluated via the degradation of methylene blue under UVA irradiation. According to the results, the thermal shock process with KF did not modify the structure, the particle size and the optical properties of ZnO nanoparticles but successfully increase their UVA and visible light induced photocatalytic activity. This enhancement of activity may be attributed to the increase of surface hydroxyl groups and zinc vacancies of modified ZnO samples.     

Spectroscopic studies on iron complexes of different anthracyclines in aprotic solvent systems

Iron complexes of daunorubicin, idarubicin, pirarubicin, and doxorubicin in anhydrous DMF were studied by UV/vis, CD, fluorescence, M?ssbauer, and EPR spectroscopy. Titration studies of the metal-free anthracyclines showed one (UV-detectable) deprotonation step requiring 2 equiv of base, compared to 1 equiv for quinizarine. Metal complexation was studied at three different metal/ligand ratios, and with increasing amounts of base. The results obtained from optical spectroscopy show the existence of two different complex species and give clear indications for the requirements of metal complexation. Complex species I, formed at a low iron-to-ligand ratio, is less dependent on base addition than complex species II formed with equimolar ferric ion. EPR and M?ssbauer experiments provide further insight into the structures of both complex species. Lack of spin density of the M?ssbauer samples in EPR indicates spin coupling between the metal centers. M?ssbauer spectra consist of single quadrupole doublets with values typical for high-spin ferric ion in an octahedral arrangement. The M?ssbauer spectroscopic features at 7 T exclude the presence of S = 0 dimers. Complex I represents a monomeric ferric iron complex whereas complex II is consistent with a more or less aggregrated oligomeric Fe-anthracycline system.     

Hydrogenation of Carbon Dioxide on Iron Manganese Catalysts

The synthesis of hydrocarbons from hydrogenation of carbon dioxide has been studied on a series of coprecipitated iron-manganese catalysts. Kinetic measurements, X-ray diffraction, Mössbauer spectroscopy, and temperature-programmed reaction of adsorbed species were used for activity tests and catalyst characterizations. The results showed that the yields of low-carbon olefins decrease, whereas the amount of methane increases with increasing manganese content in catalysts. The conversion to hydrocarbons is suppressed by the reverse water-gas shift (RWGS) reaction equilibrium. Mössbauer spectra and XRD patterns of catalysts after reaction indicate that catalysts are severely oxidized; it is speculated that the olefin producing surface structure in CO hydrogenation may be destroyed by this oxidation. A pulse-reactor study of the Boudouard reaction showed that manganese has the effect of suppressing CO dissociation and thus decreasing carbon content on catalysts. For CO₂ hydrogenation, the affinity to carbon on catalysts is important; therefore manganese is not a good promoter. Among all catalysts tested, pure iron has the best selectivity to olefinic and long-chain hydrocarbons.     

Effect of Manganese Incorporation Manner on an Iron-Based Catalyst for Fischer-Tropsch Synthesis

A systematic study was undertaken to investigate the effects of the manganese incorpo- ration manner on the textural properties,bulk and surface phase compositions,reduction/carburization behaviors,and surface basicity of an iron-based Fischer-Tropsch synthesis(FTS)catalyst.The cata- lyst samples were characterized by N_2 physisorption,X-ray photoelectron spectroscopy(XPS),H_2(or CO)temperature-programmed reduction(TPR),CO_2 temperature-programmed desorption(TPD),and M(?)ssbauer spectroscopy.The FTS performance of the catalysts was studied in a slurry-phase continuously stirred tank reactor(CSTR).The characterization results indicated that the manganese promoter incor- porated by using the coprecipitation method could improve the dispersion of iron oxide,and decrease the size of the iron oxide crystallite.The manganese incorporated with the impregnation method is enriched on the catalyst's surface.The manganese promoter added with the impregnation method suppresses the reduction and carburization of the catalyst in H_2,CO,and syngas because of the excessive enrichment of manganese on the catalyst surface.The catalyst added manganese using the coprecipitation method has the highest CO conversion(51.9%)and the lowest selectivity for heavy hydrocarbons(C_(12 )).     

Synthesis of gold functionalized poly-bisvinylethyleneurea/silica hybrid materials

Novel gold/poly-(1,3-divinyl-imidazolid-2-one)/silica [poly-bisvinylethyleneurea (poly-BVU)/silica)] hybrid particles have been produced by adsorption and spontaneously occurring in situ reduction of Au(3+) cations on the surface of poly-BVU/silica hybrid particles. The successful functionalization of the poly-BVU/silica particles with gold nanoclusters has been evidenced by UV/vis and XPS spectroscopy as well as scanning electron microscopy. The size of the resulting gold clusters, estimated by means of the Mie-Drude theory on the full peak width at half-maximum of the surface plasmon UV/vis absorbance, correlates with the polymer content of the poly-BVU/silica hybrid particles used for the modification. Therefore, it is possible to control the size of the gold clusters simply by adjusting the monomer/silica ratio in the polymerization process, which corresponds with the polymer content of the hybrids.     

Effect of surface hydroxyl concentration on the bonding and morphology of aminopropylsilane thin films on austenitic stainless steel

The adsorption of 3‐aminopropyltrimethoxysilane thin films on Fe? 18Cr? 7Mn? 3Ni (austenitic stainless steel) was investigated by X‐ray photoelectron spectroscopy (XPS) and inelastic electron background analysis. The bonding and morphology of the films were strongly dependent on the surface hydroxyl concentration, which was controlled by the oxidation pretreatment of the substrate. In particular, an aminopropylsilane (APS) monolayer with high degree of bonding to the substrate was obtained on an electrochemically passivated surface with very high hydroxyl concentration. On the other hand, the deposition of weakly bound APS clusters was observed on substrates having relatively low hydroxyl concentrations. The adsorption occurred initially via hydrogen bonding, whereas heating to 373 K resulted in the formation of covalent Si? O? M bonds at the silane/metal oxide interface. The results of this study provide insight into the interaction between silanes and stainless steels surfaces, and can be applied for functionalization of stainless steel materials in an extensive range of applications. Copyright © 2010 John Wiley & Sons, Ltd.     

Gold and platinum molecular cluster compounds studied by 197Au Mössbauer Spectroscopy

The technique of ¹⁹⁷Au Mössbauer absorption spectroscopy has been used to study four varieties of the high nuclearity gold molecular cluster compounds abbreviated as Au₅₅, all having a cuboctahedral structure, with 12 PPh₃-ligands or modifications of PPh₃. The technique of emission spectroscopy developed in our laboratory [1] has been applied to four different molecular platinum carbonyl cluster compounds of varying cluster nuclearity, abbreviated as Pt₃₈, Pt₂₆, Pt₂₄, and Pt₁₉ [2]. The four Au55 compounds were studied, both as dry materials and as frozen solutions. The M6ssbauer parameters of the chlorine ligated site of the water soluble version differ strongly due to the effect of Na⁺ on the Au-Cl distances. In the frozen solution, the effect of the ionic charge on this cluster can be clearly seen. The similarity of the spectra of all the Pt compounds, especially the occurrence of a substantial singlet contribution in all spectra, is explained by a coalescing mechanism for the low-nuclearity clusters, induced by the neutron irradiation damage inflicted while preparing the sample as M6ssbauer sources. The observed decrease of the absorption intensity with increasing temperature is evidence for a cluster character of the sample remaining after neutron irradiation.     

Structural, (197)Au Mössbauer and solid state (31)P CP/MAS NMR studies on bis (cis-bis(diphenylphosphino)ethylene) gold(I) complexes [Au(dppey)(2)]X for X = PF(6), I

(197)Au M?ssbauer spectra for the d(10) gold(i) phosphine complexes, [Au(dppey)(2)]X (X = PF(6), I; dppey = (cis-bis(diphenylphosphino)ethylene), and the single crystal X-ray structure and solid state (31)P CPMAS NMR spectrum of [Au(dppey)(2)]I are reported here. In [Au(dppey)(2)]I the AuP(4) coordination geometry is distorted from the approximately D(2) symmetry observed for the PF(6)(-) complex with Au-P bond lengths 2.380(2)-2.426(2) A and inter-ligand P-Au-P angles 110.63(5)-137.71(8) degrees . Quadrupole splitting parameters derived from the M?ssbauer spectra are consistent with the increased distortion of the AuP(4) coordination sphere with values of 1.22 and 1.46 mm s(-1) for the PF(6)(-) and I(-) complexes respectively. In the solid state (31)P CP MAS NMR spectrum of [Au(dppey)(2)]I, signals for each of the four crystallographically independent phosphorus nuclei are observed, with the magnitude of the (197)Au quadrupole coupling being sufficiently large to produce a collapse of (1)J(Au-P) splitting from quartets to doublets. The results highlight the important role played by the counter anion in the determination of the structural and spectroscopic properties of these sterically crowded d(10) complexes.     

Surface modification of microporous polypropylene membranes by the grafting of poly(γ-stearyl-l-glutamate)

A polypeptide, poly(γ-stearyl-l-glutamate) (PSLG), was grafted on the surface of hydrophobic polypropylene hollow fiber membranes through the ring opening polymerization of N-carboxyanhydride (NCA) of γ-stearyl-l-glutamate initiated by amino groups which was generated by ammonia plasma. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), together with water contact angle and bovium serum albumin adsorption measurements were used to characterize the modified membrane surface. The XPS and FT-IR spectra demonstrated that polypeptide was actually grafted on the membrane surface despite of the low degree of graft polymerization due to the hydroxyl groups on the membrane surface. To subject the ammonia plasma-treated membrane with γ-(aminopropyl)triethanoxysilane (γ-APS) which can react with hydroxyl groups and leave amino groups, the degree of graft polymerization could be improved. The bovium serum albumin adsorption measurement was conducted to further examine the surface properties of modified and original membranes. Potential applications of the PSLG grafted membranes are expected for enantiomer separation and/or enzyme immobilization.     

Highly crystalline strontium ferrites SrFeO(3-δ): an easy and effective wet-chemistry synthesis

The synthesis of strontium ferrite SrFeO(3-δ) has been explored through wet-chemistry methods in order to optimize a quick, easy and reproducible method to obtain the perovskite in pure crystalline form with a high yield. Among the three investigated synthetic paths, (i) coprecipitation of hydroxides, (ii) coprecipitation of oxalates and (iii) polyol-assisted coprecipitation, only the second one was effective in obtaining the desired perovskite modification as a single phase. The products were analyzed by means of powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), to determine the crystalline structure and the chemical composition of the sample surface, respectively, and to optimise the synthetic process. Pure samples were further characterised by means of inductively coupled plasma (ICP-AES) analysis, nitrogen adsorption, elemental analysis, temperature programmed reduction (TPR) and M?ssbauer spectroscopy.     

Zeolite‐Supported Gold Nanoparticles for Selective Photooxidation of Aromatic Alcohols under Visible‐Light Irradiation

With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99 %) under visible‐light irradiation at ambient temperature. Au/zeolite photocatalysts were characterised by UV/Vis, X‐ray photoelectron spectroscopy (XPS), TEM, XRD, energy‐dispersive spectroscopy (EDS), Brauner–Emmet–Teller (BET) analyses, IR and Raman techniques. The surface plasmon resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible‐light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterisation data and the photocatalytic performances, we proposed a possible photooxidation mechanism.     

Photosensitive Azopolymer Brushes via Atom Transfer Radical Polymerization for Protein Sensing

Novel photosensitive azopolymer brushes were synthesized via surface initiated atom transfer radical polymerization using initiator self‐assembled on Au surface. The chemical structures of azobenzene derivatives were confirmed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). The surface morphology of azopolymers via atom transfer radical polymerization (ATRP) for different time was investigated by atomic force microscopy (AFM). Additionally, the photoisomerization of azopolymer was measured by ultraviolet‐visible spectroscopy (UV‐Vis). The results indicate that such azopolymers can undergo trans‐cis‐trans photoisomerization efficiently by photo‐irradiation with UV light. Furthermore, this photoisomerization property could also induce the reversible adsorption of bovine serum albumin (BSA) adsorption on azopolymer brush surfaces. This adsorption kinetics of the reversible process can be measured by surface plasmon resonance (SPR) spectroscopy in situ. It suggests that the protein biochips could be regenerated safely by UV irradiation rather than by being rinsed with chemical reagents.     

Oxidative Transformations of Phenylacetylene on a Manganese(IV) Oxide Adsorbent-Catalyst

It is shown by IR spectroscopy and thermally programmed surface reactions that the complete oxidation of phenylacetylene on hydrated manganese dioxide in an adsorption catalytic regime occurs via dissociation of the CC bond (during chemisorption) with the formation of formate and benzoate on the surface.     

Dioxygen activation at non-heme diiron centers: characterization of intermediates in a mutant form of toluene/o-xylene monooxygenase hydroxylase

We report the generation and characterization of an intermediate in a mutant form of the toluene/o-xylene monooxygenase hydroxylase component from Pseudomonas stutzeri OX1. The reaction of chemically reduced I100W variant in the presence of the coupling protein, ToMOD, with dioxygen was monitored by stopped-flow UV/visible spectroscopy. Rapid-freeze quench (RFQ) samples were also generated for EPR and M?ssbauer spectroscopy. A transient species is observed in the UV/visible spectrum with an absorption maximum at 500 nm. EPR and M?ssbauer spectra of RFQ samples identified this species as a diiron(III,IV) cluster spin-coupled to a neutral W radical. A diamagnetic precursor to the mixed-valent diiron(III,IV) was also observed at an earlier time point, with M?ssbauer parameters typical of high-spin FeIII. We have tentatively assigned this antiferromagnetically coupled diiron(III) intermediate as a peroxo-bridged cluster, and this complex has also been observed in preliminary studies of the wild-type hydroxylase.     

A simple approach for preparing a visible-light TiO2 photocatalyst

The surface of titanium dioxide nanoparticles has been chemically modified with toluene 2,4-di-isocyanate (TDI). The modified titanium dioxide can efficiently absorb visible irradiation. The samples were characterized by means of wide-angle X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), diffuse reflectance UV–Vis spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA). The as-prepared photocatalyst exhibited good photostability and photocatalytic performance in the degradation of organic compounds. For model organic pollutants, modified titanium dioxide had excellent visible-light photocatalytic performance and the surface chemistry linkage product had high photostability.     

可循环使用的Sn-TiO2/聚噻吩纳米杂化材料用于可见光下降解有机污染物

采用改进的溶胶-凝胶法在低温制备了Sn-TiO2/聚噻吩纳米杂化材料(SPNH),运用X射线衍射(XRD)、扫描电镜、X射线光电子能谱(XPS)、红外光谱(IR)、紫外-可见光漫反射光谱(UV-DRS)和BET比表面积分析对所制样品进行了表征。 XRD结果证实聚噻吩(PTh)对TiO2晶相结构没有影响。 IR和UV-DRS结果表明,在掺杂的金属氧化物与PTh的纳米杂化和结合过程中, PTh表面与金属氧化物之间存在相互作用(类似核壳结构)。 XPS结果显示,纳米杂化材料中存在Sn4+以及PTh与TiO2各自所含的元素。催化剂表面吸附污染物结果发现, SPNH的吸附容量高于Sn-TiO2纳米粒子(STN)。在可见光下降解有机污染物硝基苯(NB)和孔雀绿(MG)的反应中, SPNH表现出比单纯STN更高的光催化活性和稳定性。由于STN上存在聚噻吩,使得样品表面吸附NB(24%)和MG(21%)的能力增加,从而导致更高的光催化收率。考察了该光催化剂在可见光下重复使用5次时的光催化活性,未见PTh的消耗和降解。这些高光催化活性的SPNH材料有望在工业水净化中用作光催化剂。     

Azobenzene-containing triazatriangulenium adlayers on Au(111): structural and spectroscopic characterization

Adlayers of different azobenzene-functionalized derivatives of the triazatriangulenium (TATA) platform on Au(111) surfaces were studied by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), gap-mode surface-enhanced Raman spectroscopy (gap-mode SERS), and cyclic voltammetry (CV). The chemical composition of the adlayers is in good agreement with the molecular structure, i.e., different chemical groups attached to the azobenzene functionality were identified. Furthermore, the presence of the azobenzene moieties in the adlayers was verified by the vibration spectra and electrochemical data. These results indicate that the molecules remain intact upon adsorption with the freestanding functional groups oriented perpendicularly to the TATA platform and thus also to the substrate surface.