共查询到20条相似文献,搜索用时 15 毫秒
1.
Yan YG Li QX Huo SJ Ma M Cai WB Osawa M 《The journal of physical chemistry. B》2005,109(16):7900-7906
A versatile two-step wet process to fabricate Pt, Pd, Rh, and Ru nanoparticle films (simplified as nanofilms hereafter) for in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) study of electrochemical interfaces is presented, which incorporates an initial chemical deposition of a gold nanofilm on the basal plane of a silicon prism with the subsequent electrodepostion of desired platinum group metal overlayers. Galvanostatic electrodeposition of Pt, Rh, and Pd from phosphate or perchloric acid electrolytes, or potentiostatic electrodeposition of Ru from a sulfuric acid electrolyte, yields sufficiently "pinhole-free" overlayers as evidenced by electrochemical and spectroscopic characterizations. The Pt group metal nanofilms thus obtained exhibit strongly enhanced IR absorption. In contrast to the corresponding metal films electrochemically deposited directly on glassy carbon and bulk metal electrodes, the observed enhanced absorption for the probe molecule CO exhibits normal unipolar band shapes. Scanning tunneling microscopic (STM) images reveal that fine nanoparticles of Pt group metals are deposited around wavy and stepped bunches of Au nanoparticles of relatively large sizes. This ubiquitous strategy is expected to open a wide avenue for extending ATR surface-enhanced IR absorption spectroscopy to explore molecular adsorption and reactions on technologically important transition metals, as exemplified by successful real-time spectroscopic and electrochemical monitoring of the oxidation of CO at Pd and that of methanol at Pt nanofilm electrodes. The spectral features of free water molecules coadsorbed with CO on Pt, Pd, Rh, and Ru are also discussed. 相似文献
2.
S. Cramm K. A. Friedrich K.-P. Geyzers U. Stimming R. Vogel 《Analytical and bioanalytical chemistry》1997,358(1-2):189-192
Electrochemical Ru deposits on Pt(111) surfaces are investigated by STM; the images of the Ru-modified surfaces show islands
of monoatomic height and between 2–5 nm in diameter. The density of islands on the surface depends on the Ru deposition potential
(observed by STM and XRSD) and the cyclic voltammograms indicate an increasing Ru coverage for lower deposition potentials.
The Ru surface coverage is determined by ex-situ XPS measurements and a linear dependence of the Ru coverage on the deposition
potential is demonstrated. IR spectra of a monolayer of adsorbed CO on the Ru-modified Pt(111) surfaces show distinct bands
for CO adsorbed on Pt and on Ru. For the integrated band intensity of the CO/Ru vibration a linear dependence on deposition
potential is found indicating that lateral dipole interactions between CO adsorbed on Pt and Ru are unimportant and that the
CO coverage on the Ru islands is constant for the Ru coverages investigated. The possibility of using adsorbate vibrational
bands for the determination of the coverage of deposits is discussed.
Received: 24 June 1996 / Revised: 6 December 1996 / Accepted: 12 December 1996 相似文献
3.
Electrooxidation of carbon monoxide and methanol on platinum-overlayer-coated gold nanoparticles: effects of film thickness 总被引:1,自引:0,他引:1
The electrooxidation of carbon monoxide and methanol on Pt-coated Au nanoparticles attached to 3-aminopropyl trimethoxysilane-modified indium tin oxide electrodes was examined as a function of Pt film thickness and Au particle coverage. For the electrodes with medium and high Au particle coverages, the CO stripping peak position shifts to more negative values with increasing Pt film thickness, from ca. 0.8 V (vs Ag/AgCl) at 1 ML to 0.45 V at 10 ML. Accompanying this peak potential shift is the sharpening of the peak width from more than 150 to 65 mV. For the electrode with low Au particle coverage, similar peak width narrowing was also observed, but the peak potential shift is much smaller, from 0.85 V at 1 ML of Pt to 0.65 V at 10 ML. These observations are compared with the CO oxidation on bulk Pt electrodes and on Pt films deposited on bulk Au electrodes. The film-thickness-dependent CO oxidation is explained by d band theory in terms of strain and ligand effects, the particle size effect, and the particle aggregation induced by Pt film growth. Corresponding to the increasing CO oxidation activity, the current density of methanol oxidation grows with the Pt film thickness. The peak potential and current density reach the same values as those obtained on a polycrystalline bulk Pt electrode when more than 4 ML of Pt is deposited on the Au particle electrodes with a particle coverage higher than 0.25. These results suggest that it is feasible to reduce Pt loading in methanol fuel cells by using Pt thin films as the anode catalyst. 相似文献
4.
5.
Hirotaka Furukawa Katsuhiro Ajito Machiko Takahashi Masatoki Ito 《Journal of Electroanalytical Chemistry》1990,280(2)
CO adsorbed on UPD and OPD (under- and overpotential deposited) Ag layers on a Pt electrode surface was studied by SERS and IRRAS in conjunction with cyclic voltammetry. Electrochemical activation of a uniform UPD Ag adlayer produced Ag clusters on the Pt electrode as well as bare Pt sites. The strong adsorption of CO on the UPD Ag/Pt electrode compared with a bulk Ag electrode is explained by the influence of the substrate Pt atoms. The degree of electron back-donation to CO increases the degree of lower frequency shifts of CO on the electrodes in the order Pt electrodes < monolayer Ag/Pt < multilayer Ag/Pt. 相似文献
6.
Cuesta A 《Journal of the American Chemical Society》2006,128(41):13332-13333
We have used cyanide-modified Pt(111) electrodes to investigate the size and geometry of the minimum atomic ensemble necessary for the oxidation of methanol on Pt electrodes. Poison formation on cyanide-modified Pt(111) is completely inhibited, the corresponding electrooxidation reaction proceeding, hence, exclusively through the reactive intermediate pathway. These results suggest that formation of adsorbed CO would require the presence of at least three contiguous Pt atoms. 相似文献
7.
In-situ scanning tunneling microscopy (STM), cyclic voltammetry (CV), and infrared reflection-adsorption spectroscopy (IRRAS) have been used to examine the electrodeposition of gold onto Pt(111) electrodes modified with benzenethiol (BT) and benzene-1,2-dithiol (BDT) in 0.1 M HClO4 containing 10 microM HAuCl4. Both BT and BDT were attached to Pt(111) via one sulfur headgroup. STM and IRRAS results indicated that the other SH group of BDT was pendant in the electrolyte. Both BT and BDT formed (2 x 2) structures at the coverage of 0.25, and they were transformed into (square root(3) x square root(3))R30 degrees as the coverage was raised to 0.33. These two organic surface modifiers resulted in 3D and 2D gold islands at BT- and BDT-coated Pt(111) electrodes, respectively. The pendant SH group of BDT could interact specifically with gold adspecies to immobilize gold adatoms on the Pt(111) substrate, which yields a 2D growth of gold deposition. Molecular resolution STM revealed an ordered array of (6 x 2 square root(13)) after a full monolayer of gold was plated on the BDT/Pt(111) electrode. Since BDT was strongly adsorbed on Pt(111), gold adatoms only occupied free sites between BDT admolecules on Pt(111). This is supported by a stripping voltammetric analysis, which reveals no reductive desorption of BDT admolecules at a gold-deposited BDT/Pt(111) electrode. It seems that the BDT adlayer acted as the template for gold deposit on Pt(111). In contrast, a BT adlayer yielded 3D gold deposit on Pt(111). This study demonstrates unambiguously that organic surface modifiers could contribute greatly to the electrodeposition of metal adatoms. 相似文献
8.
《Electrochemistry communications》2005,7(10):1039-1044
Formic acid oxidation at platinum electrochemically deposited on polished (GC/Pt) and oxidized glassy carbon (GCox/Pt) was examined with the objective of studying the effect of electrochemical treatment of the support on deposition of platinum and on the activity of Pt catalyst. The electrodes were characterised by STM and XPS techniques. The oxidative treatment of the support leads to deposition of smaller Pt particles in comparison with the one on the polished substrate. The XPS spectra indicated the increased fraction of functional (acidic) groups on the treated support as well as the higher fraction of oxygen containing species on Pt catalyst deposited on oxidised referring to Pt deposited on polished substrate.The activity of GCox/Pt electrode is increased by the factor of 2–4 for formic acid oxidation compared to the activity of GC/Pt electrode. This result is explained by the oxidative removal of COad species leading to enhanced amount of Pt free sites available for direct formic acid oxidation to CO2. 相似文献
9.
Johnston CM Strbac S Lewera A Sibert E Wieckowski A 《Langmuir : the ACS journal of surfaces and colloids》2006,22(19):8229-8240
Catalytic activity of the Pt(111)/Os surface toward methanol electrooxidation was optimized by exploring a wide range of Os coverage. Various methods of surface analyses were used, including electroanalytical, STM, and XPS methods. The Pt(111) surface was decorated with nanosized Os islands by spontaneous deposition, and the Os coverage was controlled by changing the exposure time to the Os-containing electrolyte. The structure of Os deposits on Pt(111) was characterized and quantified by in situ STM and stripping voltammetry. We found that the optimal Os surface coverage of Pt(111) for methanol electrooxidation was 0.7 +/- 0.1 ML, close to 1.0 +/- 0.1 Os packing density. Apparently, the high osmium coverage Pt(111)/Os surface provides more of the necessary oxygen-containing species (e.g., Os-OH) for effective methanol electrooxidation than the Pt(111)/Os surfaces with lower Os coverage (vs e.g., Ru-OH). Supporting evidence for this conjecture comes from the CO electrooxidation data, which show that the onset potential for CO stripping is lowered from 0.53 to 0.45 V when the Os coverage is increased from 0.2 to 0.7 ML. However, the activity of Pt(111)/Os for methanol electrooxidation decreases when the Os coverage is higher than 0.7 +/- 0.1 ML, indicating that Pt sites uncovered by Os are necessary for sustaining significant methanol oxidation rates. Furthermore, osmium is inactive for methanol electrooxidation when the platinum substrate is absent: Os deposits on Au(111), a bulk Os ingot, and thick films of electrodeposited Os on Pt(111), all compare poorly to Pt(111)/Os. We conclude that a bifunctional mechanism applies to the methanol electrooxidation similarly to Pt(111)/Ru, although with fewer available Pt sites. Finally, the potential window for methanol electrooxidation on Pt(111)/Os was observed to shift positively versus Pt(111)/Ru. Because of the difference in the Os and Ru oxophilicity under electrochemical conditions, the Os deposit provides fewer oxygen-containing species, at least below 0.5 V vs RHE. Both higher coverage of Os than Ru and the higher potentials are required to provide a sufficient number of active oxygen-containing species for the effective removal of the site-blocking CO from the catalyst surface when the methanol electrooxidation process occurs. 相似文献
10.
Pt-Ru合金薄膜的电沉积制备及其电化学表面增强红外吸收光谱 总被引:1,自引:0,他引:1
在1mmol·L-1H2PtCl6+1mmol·L-1RuCl3+0.1mol·L-1H2SO4镀液中采用电沉积法在化学镀金膜的红外窗口Si反射面上制备Pt50Ru50合金电极.利用原子力显微镜(AFM)可以观察到制备的Pt50Ru50合金电极形貌呈现出100-200nm大小的颗粒.常规电化学分析方法得出该电极具有典型的合金特征,对CO和CH3OH具有很好的催化氧化作用.应用电化学现场衰减全反射表面增强红外光谱法(ATR-SEIRAS)可以观察到该电极上Pt位和Ru位上CO的振动谱峰,且表现出Pt-Ru二元金属良好的协同催化性能. 相似文献
11.
Zhang B Li JF Zhong QL Ren B Tian ZQ Zou SZ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7449-7455
Core-shell Au-Pt nanoparticles were synthesized by using a seed growth method and characterized by transmission electron microscopy, X-ray diffraction, and UV-vis spectroscopy. Au(core)-Pt(shell)/GC electrodes were prepared by drop-coating the nanoparticles on clean glassy carbon (GC) surfaces, and their electrochemical behavior in 0.5 M H2SO4 revealed that coating of the Au core by the Pt shell is complete. The electrooxidation of carbon monoxide and methanol on the Au(core)-Pt(shell)/GC was also examined, and the results are similar to those obtained on a bulk Pt electrode. High quality surface-enhanced Raman scattering (SERS) spectra of both adsorbed CO and thiocyanate were observed on the Au(core)-Pt(shell)/GC electrodes. The potential-dependent SERS features resemble those obtained on electrochemically roughened bulk Pt or Pt thin films deposited on roughened Au electrodes. For thiocyanate, the C-N stretching frequency increases with the applied potential, yielding two distinctly different dnu(CN)/dE. From -0.8 to -0.2 V, the dnu(CN)/dE is ca. 50 cm(-1)/V, whereas it is 90 cm(-1)/V above 0 V. The bandwidth along with the band intensity increases sharply above 0 V. At the low-frequency region, Pt-NCS stretching mode at 350 cm(-1) was observed at the potentials from -0.8 to 0 V, whereas the Pt-SCN mode at 280 cm(-1) was largely absent until around 0 V and became dominant at more positive potentials. These potential-dependent spectral transitions were attributed to the adsorption orientation switch from N-bound dominant at the negative potential region to S-bound at more positive potentials. The origin of the SERS activity of the particles is briefly discussed. The study demonstrates a new method of obtaining high quality SERS on Pt-group transition metals, with the possibility of tuning SERS activity by varying the core size and the shell thickness. 相似文献
12.
Seidel YE Lindström R Jusys Z Cai J Wiedwald U Ziemann P Behm RJ 《Langmuir : the ACS journal of surfaces and colloids》2007,23(10):5795-5801
Novel, nanostructured, carbon-supported Pt model electrodes with homogeneously distributed Pt nanoparticles of uniform size were fabricated and analyzed with respect to their electrochemical properties. For this purpose, Pt-salt-loaded micelles were deposited on a glassy carbon substrate and subsequently exposed to an oxygen plasma and a H2 atmosphere for removal of the polymer carriers and reduction of the Pt salt. The morphology of the resulting nanoparticles and their electrochemical/electrocatalytic properties were characterized by high-resolution scanning electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, and differential electrochemical mass spectrometry for CO electrooxidation. The data demonstrate that this method is generally suited to the production of nanostructured model electrodes with well-defined and independently adjustable particle size and interparticle distance distributions, which are specifically suited for quantitative studies of transport processes in electrocatalytic reactions. 相似文献
13.
Min Su Jin-Chao Dong Dr. Jia-Bo Le Yu Zhao Wei-Min Yang Prof. Zhi-Lin Yang Prof. Gary Attard Dr. Guo-Kun Liu Prof. Jun Cheng Dr. Yi-Min Wei Prof. Zhong-Qun Tian Prof. Jian-Feng Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23760-23764
The adsorption and electrooxidation of CO molecules at well-defined Pt(hkl) single-crystal electrode surfaces is a key step towards addressing catalyst poisoning mechanisms in fuel cells. Herein, we employed in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) coupled with theoretical calculation to investigate CO electrooxidation on Pt(hkl) surfaces in acidic solution. We obtained the Raman signal of top- and bridge-site adsorbed CO* molecules on Pt(111) and Pt(100). In contrast, on Pt(110) surfaces only top-site adsorbed CO* was detected during the entire electrooxidation process. Direct spectroscopic evidence for OH* and COOH* species forming on Pt(100) and Pt(111) surfaces was afforded and confirmed subsequently via isotope substitution experiments and DFT calculations. In summary, the formation and adsorption of OH* and COOH* species plays a vital role in expediting the electrooxidation process, which relates with the pre-oxidation peak of CO electrooxidation. This work deepens knowledge of the CO electrooxidation process and provides new perspectives for the design of anti-poisoning and highly effective catalysts. 相似文献
14.
Rodríguez P Herrero E Aldaz A Feliu JM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(25):10329-10337
Irreversibly adsorbed tellurium has been studied as a probe to quantify ordered domains in platinum electrodes. The surface redox process of adsorbed tellurium on the Pt(111) electrode and Pt(111) stepped surfaces takes place around 0.85 V in a well-defined peak. The behavior of this redox process on the Pt(111) vicinal surfaces indicates that the tellurium atoms involved in the redox process are only those deposited on the (111) terrace sites. Moreover, the corresponding charge density is proportional to the number of sites on (111) ordered domains (terraces) that are, at least, three atoms wide. Hence, this charge density can be used to measure the number of (111) terrace sites on any given platinum sample. Structural information about tellurium adsorption is obtained from atomic-resolution STM images for the Pt(111) and Pt(10, 10, 9) electrodes. A rectangular structure (2 x radical 3) and a compact hexagonal structure (11 x 8) were identified. However, the redox peak for adsorbed tellurium on (100) domains at 1.03 V overlaps with peaks arising from steps and (110) sites. Therefore, it cannot be used without problems for the determination of (100) sites on a platinum sample. On the (100) terraces, the surface structure of the adsorbed tellurium is c(2 x 2), as revealed by STM. Finally, tellurium irreversible adsorption has been used to estimate the number of (111) ordered domains terrace sites on different polycrystalline platinum samples, and the results are compared to those obtained with bismuth irreversible adsorption. 相似文献
15.
B. I. Podlovchenko Yu. M. Maksimov T. D. Gladysheva E. A. Kolyadko 《Russian Journal of Electrochemistry》2000,36(7):731-735
Steady-state current densities of electrooxidation of CH3OH, HCOOH, and CO at the Pt-PAN-GC electrodes (where PAN and GC stand for polyaniline and glassy carbon, respectively) and
those of electrooxidation of HCOOH at the Pd-PAN-GC electrodes are measured (per cm2 of the true metal-catalyst surface area). The found higher activity of Pt and Pd particles incorporated in PAN, as compared
with Pt/Pt and Pd/Pt, is attributed to interaction between metal-catalyst particles and the polymeric matrix. The activation
effect is the most pronounced for the HCOOH electrooxidation at Pd-PAN-GC. The data concerning hydrogen evolution testify
in favor of a decrease in exchange currents of this reaction upon going from Pt to Pt-PAN-GC electrodes 相似文献
16.
CO和SCN~-在高分散Pt及Pd表面异常红外光学行为的电化学现场FTIR反射光谱研究 总被引:2,自引:0,他引:2
在玻碳基底上沉积Pt和Pd,在以CO和SCN-为探针分子的电化学现场FTIR反射光谱研究中,首次观察到异常红外光学行为,其中包括吸附物种的谱带方向倒反以及谱峰强度显著增强等. 相似文献
17.
利用电化学衰减全反射原位傅里叶变换红外光谱与微分电化学质谱联用技术,在流动电解池环境以及恒电位条件下研究了Pt电极和Pt电极通过表面电沉积Ru形成的PtRu电极(PtxRuy)上发生的甲醇氧化反应(反应电解质溶液为0.1 mol/L HClO4+0.5 mol/L MeOH). 在0.3-0.6 V(参比电极为可逆氢参比)实验用到的所有电极上,CO是唯一能从红外光谱观察到的与甲醇相关的表面吸附物;在Pt0.56Ru0.44电极上可以观察到CO吸附在Ru原子形成的岛上和CO线式吸附在Pt电极表面红外波段,而其他电极上只能观察到Pt表面上线式吸附的CO;甲醇氧化活性按Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt的顺序递减;在0.5V时,甲醇在Pt0.73Ru0.27电极上的氧化反应的CO2电流效率达到了50%. 相似文献
18.
《Journal of Electroanalytical Chemistry》1986,198(1):137-148
The first stages of the electrooxidation of CO previously adsorbed on polycrystalline Pt in 1 M HClO4 at 25°C were investigated by means of the triangularly modulated triangular potential sweep technique. Runs were made with a Pt surface covered either partially or completely with adsorbed CO over a wide range of frequency and amplitude of the modulating signal. Reactions between the strongly and the weakly bonded adsorbed oxygen-containing adsorbed species with the linear and the bridge forms of adsorbed CO were followed via the voltammetric measurements. The kinetics of the various possible processes are discussed in terms of previous results on the voltammetric electrooxidation of adsorbed CO and on the early stages of O-electroadsorption on Pt. CO adsorption on Pt produces a change in the apparent electrode capacity which is interpreted in terms of the structure of the inner part of the electrical double layer. 相似文献
19.
Alexandre Ponrouch Sébastien Garbarino Daniel Guay 《Electrochemistry communications》2009,11(4):834-837
Platinum was electrochemically deposited in the forms of nanowires and nanotubes and compared to Pt black and Pt wire electrodes. The resistance to CO poisoning was measured in CO saturated solution by recording the current decrease in the H adsorption/desorption region through continuous sweeping of the electrode potential between 0.00 and 0.45 V vs RHE. For Pt deposits prepared with the same deposition charge, it is shown that the maximum coverage of CO, θCO,max, decreases as one goes from Pt black, to nanowires and to nanotubes. In the case of the longest nanotube prepared, θCO,max is as low as 0.44. 相似文献