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1.
Effects of Adsorbate Coverage and Bond‐Length Disorder on the d‐Band Center of Carbon‐Supported Pt Catalysts
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Dr. Matthew W. Small Dr. Joshua J. Kas Dr. Kristina O. Kvashnina Prof. Dr. John J. Rehr Prof. Dr. Ralph G. Nuzzo Prof. Dr. Moniek Tromp Prof. Dr. Anatoly I. Frenkel 《Chemphyschem》2014,15(8):1569-1572
Determination of the factors that affect the d‐band center of catalysts is required to explain their catalytic properties. Resonant inelastic X‐ray scattering (RIXS) enables direct imaging of electronic transitions in the d‐band of Pt catalysts in real time and in realistic environmental conditions. Through a combination of in situ, temperature‐resolved RIXS measurements and theoretical simulations we isolated and quantified the effects of bond‐length disorder and adsorbate coverage (CO and H2) on the d‐band center of 1.25 nm size Pt catalysts supported on carbon. We found that the decrease in adsorbate coverage at elevated temperatures is responsible for the d band shifts towards higher energies relative to the Fermi level, whereas the effect of the increase in bond‐length disorder on the d‐band center is negligible. Although these results were obtained for a specific case of non‐interacting support and weak temperature dependence of the metal–metal bond length in a model catalyst, this work can be extended to a broad range of real catalysts. 相似文献
2.
Probing Long‐Lived Plasmonic‐Generated Charges in TiO2/Au by High‐Resolution X‐ray Absorption Spectroscopy
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Dr. Lucia Amidani Dr. Alberto Naldoni Dr. Marco Malvestuto Dr. Marcello Marelli Dr. Pieter Glatzel Dr. Vladimiro Dal Santo Prof. Federico Boscherini 《Angewandte Chemie (International ed. in English)》2015,54(18):5413-5416
3.
Ultrathin Hexagonal Hybrid Nanosheets Synthesized by Graphene Oxide‐Assisted Exfoliation of β‐Co(OH)2 Mesocrystals
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Dr. Suzi Deng Dr. Christie Thomas Cherian Xiao li Liu Hui Ru Tan Li Hsia Yeo Dr. Xiaojiang Yu Prof. Andrivo Rusydi Prof. B. V. R. Chowdari Prof. Hai Ming Fan Prof. Chorng Haur Sow 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12444-12452
In the present study, we report the synthesis of a high‐quality, single‐crystal hexagonal β‐Co(OH)2 nanosheet, exhibiting a thickness down to ten atomic layers and an aspect ratio exceeding 900, by using graphene oxide (GO) as an exfoliant of β‐Co(OH)2 nanoflowers. Unlike conventional approaches using ionic precursors in which morphological control is realized by structure‐directing molecules, the β‐Co(OH)2 flower‐like superstructures were first grown by a nanoparticle‐mediated crystallization process, which results in large 3D superstructure consisting of ultrathin nanosheets interspaced by polydimethoxyaniline (PDMA). Thereafter, β‐Co(OH)2 nanoflowers were chemically exfoliated by surface‐active GO under hydrothermal conditions into unilamellar single‐crystal nanosheets. In this reaction, GO acts as a two‐dimensional (2D) amphiphile to facilitate the exfoliation process through tailored interactions between organic and inorganic molecules. Meanwhile, the on‐site conjugation of GO and Co(OH)2 promotes the thermodynamic stability of freestanding ultrathin nanosheets and restrains further growth through Oswald ripening. The unique 2D structure combined with functionalities of the hybrid ultrathin Co(OH)2 nanosheets on rGO resulted in a remarkably enhanced lithium‐ion storage performance as anode materials, maintaining a reversible capacity of 860 mA h g?1 for as many as 30 cycles. Since mesocrystals are ubiquitous and rich in morphological diversity, the strategy of the GO‐assisted exfoliation of mesocrystals developed here provides an opportunity for the synthesis of new functional nanostructures that could bear importance in clean renewable energy, catalysis, photoelectronics, and photonics. 相似文献
4.
The recent advances in the study of light emission from matter induced by synchrotron radiation: X‐ray excited optical luminescence (XEOL) in the energy domain and time‐resolved X‐ray excited optical luminescence (TRXEOL) are described. The development of these element (absorption edge) selective, synchrotron X‐ray photons in, optical photons out techniques with time gating coincide with advances in third‐generation, insertion device based, synchrotron light sources. Electron bunches circulating in a storage ring emit very bright, widely energy tunable, short light pulses (<100 ps), which are used as the excitation source for investigation of light‐emitting materials. Luminescence from silicon nanostructures (porous silicon, silicon nanowires, and Si–CdSe heterostructures) is used to illustrate the applicability of these techniques and their great potential in future applications. 相似文献
5.
Fe K‐Edge X‐ray Absorption Fine Structure Determination of γ‐Al2O3‐Supported Iron‐Oxide Species
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Dr. Atsuko Tomita Dr. Takeshi Miki Takeru Tango Tatsuro Murakami Hideyuki Nakagawa Dr. Yutaka Tai 《Chemphyschem》2015,16(9):2015-2020
The structure of FeOx species supported on γ‐Al2O3 was investigated by using Fe K‐edge X‐ray absorption fine structure (XAFS) and X‐ray diffraction (XRD) measurements. The samples were prepared through the impregnation of iron nitrate on Al2O3 and co‐gelation of aluminum and iron sulfates. The dependence of the XRD patterns on Fe loading revealed the formation of α‐Fe2O3 particles at an Fe loading of above 10 wt %, whereas the formation of iron‐oxide crystals was not observed at Fe loadings of less than 9.0 wt %. The Fe K‐edge XAFS was characterized by a clear pre‐edge peak, which indicated that the Fe?O coordination structure deviates from central symmetry and that the degree of Fe?O?Fe bond formation is significantly lower than that in bulk samples at low Fe loading (<9.0 wt %). Fe K‐edge extended XAFS oscillations of the samples with low Fe loadings were explained by assuming an isolated iron‐oxide monomer on the γ‐Al2O3 surface. 相似文献
6.
Inside Cover: Ultrathin Hexagonal Hybrid Nanosheets Synthesized by Graphene Oxide‐Assisted Exfoliation of β‐Co(OH)2 Mesocrystals (Chem. Eur. J. 39/2014)
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Dr. Suzi Deng Dr. Christie Thomas Cherian Xiao li Liu Hui Ru Tan Li Hsia Yeo Dr. Xiaojiang Yu Prof. Andrivo Rusydi Prof. B. V. R. Chowdari Prof. Hai Ming Fan Prof. Chorng Haur Sow 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12326-12326
7.
Dr. Thiruvancheril G. Gopakumar Dr. Matthias Bernien Holger Naggert Dr. Francesca Matino Christian F. Hermanns Dr. Alexander Bannwarth Svenja Mühlenberend Alex Krüger Dennis Krüger Fabian Nickel Waldemar Walter Prof. Dr. Richard Berndt Prof. Dr. Wolfgang Kuch Prof. Dr. Felix Tuczek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(46):15702-15709
Submono‐, mono‐ and multilayers of the Fe(II) spin‐crossover (SCO) complex [Fe(bpz)2(phen)] (bpz=dihydrobis(pyrazolyl)borate, phen=1,10‐phenanthroline) have beenprepared by vacuum deposition on Au(111) substrates and investigated with near edge X‐ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM). As evidenced by NEXAFS, molecules of the second layer exhibit a thermal spin crossover transition, although with a more gradual characteristics than in the bulk. For mono‐ and submonolayers of [Fe(bpz)2(phen)] deposited on Au(111) substrates at room temperature both NEXAFS and STM indicate a dissociation of [Fe(bpz)2(phen)] on Au(111) into four‐coordinate complexes, [Fe(bpz)2], and phen molecules. Keeping the gold substrate at elevated temperatures ordered monolayers of intact molecules of [Fe(bpz)2(phen)] are formed which can be spin‐switched by electron‐induced excited spin‐state trapping (ELIESST). 相似文献
8.
Dr. Kripasindhu Sardar Enrico Petrucco Craig I. Hiley Dr. Jonathan D. B. Sharman Dr. Peter P. Wells Prof. Andrea E. Russell Dr. Reza J. Kashtiban Dr. Jeremy Sloan Prof. Richard I. Walton 《Angewandte Chemie (International ed. in English)》2014,53(41):10960-10964
The pyrochlore solid solution (Na0.33Ce0.67)2(Ir1?xRux)2O7 (0≤x≤1), containing B‐site RuIV and IrIV is prepared by hydrothermal synthesis and used as a catalyst layer for electrochemical oxygen evolution from water at pH<7. The materials have atomically mixed Ru and Ir and their nanocrystalline form allows effective fabrication of electrode coatings with improved charge densities over a typical (Ru,Ir)O2 catalyst. An in situ study of the catalyst layers using XANES spectroscopy at the Ir LIII and Ru K edges shows that both Ru and Ir participate in redox chemistry at oxygen evolution conditions and that Ru is more active than Ir, being oxidized by almost one oxidation state at maximum applied potential, with no evidence for ruthenate or iridate in +6 or higher oxidation states. 相似文献
9.
Dr. Masashi Nakamura Yo Nakajima Prof. Dr. Nagahiro Hoshi Dr. Hiroo Tajiri Dr. Osami Sakata 《Chemphyschem》2013,14(11):2426-2431
The oxidation processes of a Pt(111) electrode in alkaline electrolytes depend on non‐specifically adsorbed ions according to in situ X‐ray diffraction and infrared spectroscopic measurements. In an aqueous solution of LiOH, an OHad adlayer is formed in the first oxidation step of the Pt(111) electrode as a result of the strong interaction between Li+ and OHad, whereas Pt oxidation proceeds without OHad formation in CsOH solution. Structural analysis by X‐ray diffraction indicates that Li+ is strongly protective against surface roughening caused by subsurface oxidation. Although Cs+ is situated near the Pt surface, the weak protective effect of Cs+ results in irreversible surface roughening due to subsurface oxidation. 相似文献
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11.
Three‐dimensional nanostructured metallic substrates for enhanced vibrational spectroscopy are fabricated by self‐assembly. Nanostructures consisting of one to 20 depositions of 13 nm‐diameter Au nanoparticles (NPs) on Au films are prepared and characterized by means of AFM and UV/Vis reflection–absorption spectroscopy. Surface‐enhanced polarization modulation infrared reflection–absorption spectroscopy (PM‐IRRAS) is observed from Au NPs modified by the probe molecule 4‐hydroxythiophenol. The limitation of this kind of substrate for surface‐enhanced PM‐IRRAS is discussed. The surface‐enhanced Raman scattering (SERS) from the same probe molecule is also observed and the effect of the number of Au‐NP depositions on the SERS efficiency is studied. The SERS signal from the probe molecule maximizes after 11 Au‐NP depositions, and the absolute SERS intensities from different batches are reproducible within 20 %. In situ electrochemical SERS measurements show that these substrates are stable within the potential window between ?800 and +200 mV (vs. Ag/AgCl/sat. Cl?). 相似文献
12.
Xiaoxiao Xu Prof. Caihong Fang Ting Bi Zhiqing Cui Guili Zhao Xiaomin Jiang Jinwu Hu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(47):10787-10794
Plasmonic nanostructures with large absorption areas under resonant excitation have been utilized extensively in photon-assisted applications. In this work, dodecahedral Au nanobowls were first prepared by an easy and template-free method only through the introduction of H2PtCl6 and I− during the growth procedure. The Au nanobowls show electron-field enhancement due to the high curvature of the bowl edge, the open region, and dodecahedral morphology. Au/Pt nanobowls, which couple plasmonic Au and catalytic Pt, were then constructed as plasmonic electrocatalysts for methanol oxidation. The mass activity reached 497.6 mA mg−1 under visible-light illumination, which is 1.9 times that measured in the dark. Simultaneously, the electrocatalytic stability is also greatly improved under light excitation. The enhanced properties of the plasmonic Au/Pt electrocatalysts are ascribed to the synergistic effect of the plasmon-enhanced photothermal and hot-carrier effects on the basis of experimental investigations. This work thus offers an effective methodology to construct efficient plasmonic electrocatalysts for fuel cells. 相似文献
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14.
Microsecond X‐ray Absorption Spectroscopy Identification of CoI Intermediates in Cobaloxime‐Catalyzed Hydrogen Evolution
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Dr. Grigory Smolentsev Bianca Cecconi Alexander Guda Dr. Murielle Chavarot‐Kerlidou Prof. Jeroen A. van Bokhoven Dr. Maarten Nachtegaal Dr. Vincent Artero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15158-15162
Rational development of efficient photocatalytic systems for hydrogen production requires understanding the catalytic mechanism and detailed information about the structure of intermediates in the catalytic cycle. We demonstrate how time‐resolved X‐ray absorption spectroscopy in the microsecond time range can be used to identify such intermediates and to determine their local geometric structure. This method was used to obtain the solution structure of the CoI intermediate of cobaloxime, which is a non‐noble metal catalyst for solar hydrogen production from water. Distances between cobalt and the nearest ligands including two solvent molecules and displacement of the cobalt atom out of plane formed by the planar ligands have been determined. Combining in situ X‐ray absorption and UV/Vis data, we demonstrate how slight modification of the catalyst structure can lead to the formation of a catalytically inactive CoI state under similar conditions. Possible deactivation mechanisms are discussed. 相似文献
15.
Zhongrui Li Prof. Dr. Liqiu Zheng Dr. Wensheng Yan Dr. Zhiyun Pan Dr. Shiqiang Wei Prof. 《Chemphyschem》2009,10(13):2296-2304
Single‐walled carbon nanotubes (SWNTs) synthesized with different methods are investigated by using multiple characterization techniques, including Raman scattering, optical absorption, and X‐ray absorption near edge structure, along with X‐ray photoemission by following the total valence bands and C 1s core‐level spectra. Four different SWNT materials (produced by arc discharge, HiPco, laser ablation, and CoMoCat methods) contain nanotubes with diameters ranging from 0.7 to 2.8 nm. The diameter distribution and the composition of metallic and semiconducting tubes of the SWNT materials are strongly affected by the synthesis method. Similar sp2 hybridization of carbon in the oxygenated SWNT structure can be found, but different surface functionalities are introduced while the tubes are processed. All the SWNTs demonstrate stronger plasmon resonance excitations and lower electron binding energy than graphite and multiwalled carbon nanotubes. These SWNT materials also exhibit different valence‐band X‐ray photoemission features, which are considerably affected by the nanotube diameter distribution and metallic/semiconducting composition. 相似文献
16.
Shuning Li Dr. Amitava Roy Dr. Henning Lichtenberg Gregory Merchan Dr. Challa S. S. R. Kumar Prof. Dr. J. Michael Köhler 《Chemphyschem》2012,13(6):1557-1561
The micro‐segmented flow technique was applied for continuous synthesis of ZnO micro‐ and nanoparticles with short residence times of 9.4 s and 21.4 s, respectively. The obtained particles were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Small angle X‐ray scattering (SAXS) and photoluminescence spectroscopy were used to determine the size and optical properties of ZnO nanoparticles. In addition, extended X‐ray absorption fine structure (EXAFS) spectroscopy was employed to investigate local structural properties. The EXAFS measurements reveal a larger degree of structural disorder in the nanoparticles than the microparticles. These structural changes should be taken into consideration while evaluating the size‐dependent visible emission of ZnO nanoparticles. 相似文献
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18.
Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques
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Dr. Shinobu Takao Dr. Oki Sekizawa Dr. Shin‐ichi Nagamatsu Dr. Takuma Kaneko Dr. Takashi Yamamoto Dr. Gabor Samjeské Dr. Kotaro Higashi Dr. Kensaku Nagasawa Dr. Takuya Tsuji Dr. Motohiro Suzuki Dr. Naomi Kawamura Dr. Masaichiro Mizumaki Prof. Dr. Tomoya Uruga Prof. Dr. Yasuhiro Iwasawa 《Angewandte Chemie (International ed. in English)》2014,53(51):14110-14114
There is limited information on the mechanism for platinum oxidation and dissolution in Pt/C cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) under the operating conditions though these issues should be uncovered for the development of next‐generation PEFCs. Pt species in Pt/C cathode catalyst layers are mapped by a XAFS (X‐ray absorption fine structure) method and by a quick‐XAFS(QXAFS) method. Information on the site‐preferential oxidation and leaching of Pt cathode nanoparticles around the cathode boundary and the micro‐crack in degraded PEFCs is provided, which is relevant to the origin and mechanism of PEFC degradation. 相似文献
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Chemical Speciation and Bond Lengths of Organic Solutes by Core‐Level Spectroscopy: pH and Solvent Influence on p‐Aminobenzoic Acid
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Dr. Joanna S. Stevens Adrian Gainar Dr. Edlira Suljoti Dr. Jie Xiao Ronny Golnak Prof. Emad F. Aziz Prof. Sven L. M. Schroeder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):7256-7263
Through X‐ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near‐edge X‐ray absorption fine structure (NEXAFS) and resonant inelastic X‐ray scattering (RIXS) measurements at the nitrogen K‐edge of para‐aminobenzoic acid reveal both pH‐ and solvent‐dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. This provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions. 相似文献