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1.
A novel boron nitride (BN) supported Pt-Sn catalyst was used for the oxydehydrogenation of propane. BN is a graphite-like inert support which provides negligible interaction with metals. The Pt-Sn/BN catalysts were prepared by co-incipient wetness impregnation with various Sn loadings. A commercial support γ-Al2O3 was chosen to compare with BN. PtSn alloys were formed due to the partially reduced Sn in Pt-Sn/BN catalyst in H2 at 400 °C. Furthermore, the crystalline phases of PtSn and SnPt3 alloys were also observed from the XRD patterns of Pt-Sn/BN catalysts. However, PtSn alloys were not detected in Pt-Sn/γ-Al2O3 by XRD. The Sn addition clearly improved the activity and propylene selectivity of Pt-Sn/BN at 600 °C. The more the Sn loading, the higher the selectivity and yield of propylene were. A maximum yield of propylene (38.3%) was achieved on Pt-Sn (0.75 wt%)/BN catalyst at the start of reaction. The catalysts, Pt-Sn/γ-Al2O3, deactivated more rapidly than Pt-Sn/BN. The activity and selectivity enhancement are attributed to the formation of PtSn and/or SnPt3 alloy particles on the BN support. Compared with the hydrophilic γ-Al2O3, the hydrophobic BN surface can expel H2O during the oxidation of hydrogen resulting in the activity increase.  相似文献   

2.
The Pt3Sn/C catalyst with high electrochemical activity was synthesized under optimizing preparation conditions. The surface of carbon support pretreated by strong acid contains many O-H and CO groups, which will increase the active sites of PtSn/C catalysts. The catalyst structure was characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and temperature programmed reduction (TPR). The co-reduction of Pt4+ and Sn2+ ions causes Sn to enter Pt crystal lattice to form PtSn alloy whose surface, however, contains tin oxides with Sn4+ and Sn2+ valences, which can promote the ethanol oxidation. The crystallinity of PtSn decreases with the reduction of the atomic ratio of Pt:Sn. By prolonging the reaction time of formic acid, the forward anodic peak current of ethanol oxidation reaches 16.2 mA on the Pt3Sn/C catalyst with 0.025 mg Pt loading.  相似文献   

3.
In this work, well defined alumina and silica supported Pt and PtSn catalysts were prepared by surface organometallic reactions and were characterized by TEM, XPS and EXAFS. These catalysts were tested in the catalytic dehydrogenation of isobutane. XPS results show that tin is found under the form of Sn(0) and Sn(II,IV), being the percentage of Sn(0) lower for alumina supported than for silica supported catalysts. Tin modified platinum catalysts, always show a decrease of approximately 1 eV in the BE of Pt, what would be indicative of an electron charge transfer from tin to platinum. When the concentration of Sn(0) is high enough, in our case Sn(0)/Pt  0.3, EXAFS experiments demonstrated the existence of a PtSn alloy diluting metallic Pt atoms, for both PtSn/γ-Al2O3 and PtSn/SiO2. This PtSn alloy seems to be not active in the dehydrogenation reaction; however, it is very important for selectivity and stability, inhibiting cracking and coke formation reactions. The ensemble of our catalytic, XPS and EXAFS results, show that bimetallic PtSn/γ-Al2O3 catalysts, prepared via SOMC/M techniques, can be submitted to several sequential reaction–regeneration cycles, recovering the same level of initial activity each time and that the nature of the catalytic surface remains practically without modifications.  相似文献   

4.
Electrochemical activities and structural features of Pt/Sn catalysts supported by hydrogen-reduced SnO2 nanowires (SnO2NW) are studied, using cyclic voltammetry, CO stripping voltammetry, scanning electron microscopy, and X-ray diffraction analysis. The SnO2NW supports have been grown on a carbon paper which is commercially available for gas diffusion purposes. Partial reduction of SnO2NW raises the CO tolerance of the Pt/Sn catalyst considerably. The zero-valence tin plays a significant role in lowering the oxidation potential of COads. For a carbon paper electrode loaded with 0.1 mg cm−2 Pt and 0.4 mg cm−2 SnO2NW, a conversion of 54% SnO2NW into Sn metal (0.17 mg cm−2) initiates the COads oxidation reaction at 0.08 V (vs. Ag/AgCl), shifts the peak position by 0.21 V, and maximizes the CO tolerance. Further reduction damages the support structure, reduces the surface area, and deteriorates the catalytic activity. The presence of Sn metal enhances the activities of both methanol and ethanol oxidation, with a more pronounced effect on the oxidation current of ethanol whose optimal value is analogous to those of PtSn/C catalysts reported in literature. In comparison with a commercial PtRu/C catalyst, the optimal Pt/Sn/SnO2NW/CP exhibits a somewhat inferior activity toward methanol, and a superior activity toward ethanol oxidation.  相似文献   

5.
F. Wang  Y. Zheng  Y. Guo 《Fuel Cells》2010,10(6):1100-1107
Well‐dispersed PtSnEu/C and PtSn/C catalysts were prepared by the impregnation–reduction method using formic acid as a reductant and characterised by X‐ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersion X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS). The synthesised catalysts with different atomic ratios of Pt/Sn/Eu have the Pt face centered cubic (fcc) structure and their particle sizes are 3–4 nm. The PtSnEu/C catalyst is composed of many Pt (0), SnO2, Eu(OH)3, a small amount of Pt(II) and partly alloyed PtSn, but no metallic Eu. The electrochemical measurements indicate that in comparison with Pt3Sn1/C catalyst, the Pt3Sn1Eu1/C catalyst for ethanol oxidation has more negative onset potential, smaller apparent activation energy and lower electrochemical impedance so that it exhibits very high catalytic activity. Its peak current density increases by 135% and 40%, compared with Pt3Sn1/C and Pt1Ru1/C (JM) catalysts, respectively. This is because the Eu(OH)3 formed by adding Eu to PtSn/C catalyst can provide the OH group which is in favour of the removal of adsorbed intermediates and ethanol oxidation.  相似文献   

6.
Disordered alloy and bi-phase PtSn nanoparticles of nominal Pt:Sn ratio of 70:30 atomic % with controlled size and narrow size distribution were synthesized using a single-step polyol method. By adjusting the solution pH it was possible to obtain Pt7Sn3 nanoparticles of various sizes from 2.8 to 6.5 nm. We found that the presence of NaOH in the synthesis solution not only influenced the nanoparticle size, but as it was revealed by XRD, it apparently also dictated the degree of Pt and Sn alloying. Three catalysts prepared at lower NaOH concentrations (CNaOH < 0.15 M) showed disordered alloy structure of the nominal composition, while the other three catalysts synthesized at higher NaOH concentrations (CNaOH > 0.15 M) consisted of bi-phase nanoparticles comprising a crystalline phase close to that of pure Pt together with an amorphous Sn phase. These observations are plausibly due to the phase separation and formation of monometallic Pt and amorphous SnOx phases. A proposed reaction mechanism of Pt7Sn3 nanoparticle formation is presented to explain these observations along with the catalytic activities measured for the six synthesized carbon-supported Pt7Sn3 catalysts. The highest catalytic activity towards ethanol electro-oxidation was found for the carbon-supported bi-phase catalyst that formed the largest Pt (6.5 nm) nanoparticles and SnOx phase. The second best catalyst was a disordered alloy Pt7Sn3 catalyst with the second largest nanoparticle size (5 nm), while catalysts of smaller size (4.5–4.6 nm) but different structure (disordered alloy vs. bi-phase) showed similar catalytic performance inferior to that of the 5 nm disordered alloy Pt7Sn3 catalyst. This work demonstrated the importance of producing bi-metallic PtSn catalysts with large Pt surfaces in order to efficiently electro-oxidize ethanol.  相似文献   

7.
Vulcan XC-72R carbon was pretreated using acid and thermal activation methods, and the carbons obtained were used as supports for a PtSn/C catalyst synthesized by a successive reduction process. Surface characteristics of the supports, including BET surface area, pHPZC and functional group, were analyzed using physical N2 adsorption, mass titration, acid–base titration, and Fourier transform infrared (FTIR) spectrometer technique, respectively. The prepared PtSn/C catalysts were characterized by X-ray diffractometer (XRD), energy dispersive X-ray spectrometer (EDX), inductively coupled plasma–atomic emission spectrometry (ICP–AES), and transmission electron microscope (TEM) techniques, and then were examined for their behavior under ethanol oxidation as well as for their performance in a direct ethanol fuel cell (DEFC). The results showed that pretreatment by HNO3 produced various oxygenated functional groups on the support surface and increased its acidic property. The strong acidity of the acid-treated support led to an unfavorable condition for the Pt reduction reaction and resulted in low Pt content but high Pt:Sn ratio in the PtSn/C catalyst. On the other hand, thermal activation increased the base functional groups on the carbon surface, which enhanced reduction of Pt precursor, and consequently, provided a small average metal particle size of 2.2 nm. The results from cyclic voltammetry, chronoamperometry and cell performance testing confirmed that the catalytic activity for ethanol oxidation and the performance in the direct ethanol fuel cell of the heat-treated carbon-supported PtSn catalyst was superior to the fresh PtSn/C catalyst and the acid-treated carbon-supported PtSn catalyst.  相似文献   

8.
Carbon-supported binary PtSn catalysts with varied alloying degree were synthesized in different processes and denoted as PtSn/C-B, PtSn/C-EG and PtSnO2/C, respectively. X-ray diffraction (XRD) characterizations showed that PtSn/C-B catalyst displayed the highest alloying degree, while PtSnO2/C catalyst had the lowest one among these samples. X-ray photoelectron spectroscopy (XPS) results revealed that the non-alloyed Sn existed in an oxidized state on the surfaces of these catalysts. By evaluating the electro-catalytic activity and analyzing the final products of ethanol oxidation reaction (EOR) on these catalysts, it was found that PtSnO2/C catalyst enhanced the products yield of acetic acid products and PtSn/C-B catalyst promoted the entire activity for EOR. It was proposed that non-alloyed SnO2 species enhanced the bi-functional mechanism, whereas PtSn alloy phase strengthened the electronic effect of PtSn/C catalyst.  相似文献   

9.
Pt催化丙烷脱氢过程中结焦反应的粒径效应与Sn的作用   总被引:1,自引:0,他引:1  
用乙二醇还原法制备了Pt颗粒平均粒径分别为2.0、4.6、12.1 nm的Pt/Al2O3催化剂,同时用浸渍法制备了PtSn/Al2O3双金属催化剂,并考察了各催化剂在丙烷脱氢过程中的结焦行为。分别用H2化学吸附、透射电镜、热重分析、元素分析、红外光谱、拉曼光谱等手段对催化剂进行了表征。表征结果显示,催化剂金属上的结焦速率与Pt金属颗粒粒径密切相关。具有较小Pt颗粒的催化剂金属上的结焦速率明显大于具有较大Pt颗粒的催化剂。具有较小Pt颗粒的催化剂上生成的焦含有较少的氢,其石墨化程度也较高。本研究中PtSn/Al2O3催化剂金属上的结焦速率高于Pt/Al2O3催化剂,并且在双金属上生成的焦具有更高的石墨化程度。结合Pt/Al2O3催化剂上的结焦机理,对高性能丙烷脱氢催化剂提出了新的概念设计。  相似文献   

10.
Binary PtIr, PtSn and ternary PtSnIr electrocatalysts were prepared by the Pechini-Adams modified method on carbon Vulcan XC-72, and these materials were characterized by TEM and XRD. The XRD results showed that the electrocatalysts consisted of the Pt displaced phase, suggesting the formation of solid solutions between the metals Pt/Ir and Pt/Sn. However, the increase in Sn loading promoted phase separation, with the formation of peaks typical of cubic Pt3Sn. The electrochemical investigation of these different electrode materials was carried out as a function of the electrocatalyst composition, in a 0.5 mol dm−3 H2SO4 solution, with either the presence or the absence of ethanol. Cyclic voltammetric measurements and chronoamperometric results obtained at room temperature showed that PtSn/C and PtSnIr/C displayed better electrocatalytic activity for ethanol electrooxidation compared to PtIr/C and Pt/C, mainly at low potentials. The oxidation process was also investigated by in situ infrared reflectance spectroscopy, to identify the adsorbed species. Linearly adsorbed CO and CO2 were found, indicating that the cleavage of the CC bond in the ethanol substrate occurred during the oxidation process. At 90 °C, the Pt89Sn11/C and Pt68Sn9Ir23/C electrocatalysts displayed higher current and power performances as anode materials in a direct ethanol fuel cell (DEFC).  相似文献   

11.
《中国化学工程学报》2014,22(11-12):1232-1236
Dehydrogenation of propane on Pt or PtSn catalyst over Al2O3 or SBA-15 support was investigated. The catalysts were characterized by CO-pulse chemisorption, thermogravimetry, temperature-programmed-reduction of H2, and diffuse reflectance infrared Fourier transform spectroscopy of absorbed CO. The results show that the platinum species is in oxidation state in the catalyst on Al2O3 support, so the catalyst must be reduced in H2 before dehydrogenation reaction. Addition of Sn improves the Pt dispersion, but the catalyst deactivates rapidly because of the coke formation. The interaction of Pt and Al2O3 is strong. On SBA-15 support, the platinum species is completely reduced to Pt0 in the calcination process, so the reduction is not needed. Addition of Sn improves the activity and selectivity of the catalyst. The interaction of Pt and SBA-15 is weak, so it is easy for Pt particles to sinter.  相似文献   

12.
A major obstacle to the broader use of fuel cells is the poisoning of supported Pt catalysts by the CO present in virtually all feeds. In this paper, the microcalorimetry technique was employed to study and compare the CO adsorption properties of different commercial carbon-supported platinum catalysts with high Pt loading, aimed to be used in proton exchange membrane fuel cells (PEMFCs) applications. Combined with other techniques of characterization, such as BET, XRD, TPD-MS and TPR, adsorption microcalorimetry has permitted a better understanding of the studied systems. The pore architecture of Pt/C catalysts was found to influence the kinetics of heat release during CO adsorption. The accessibility of CO molecules to the adsorption sites increased with the mesoporosity of the catalyst. The degree of catalyst poisoning by CO upon successive air/H2/CO cycles varied between 2 and 30% for the different studied samples. These results confirm that the surface chemistry of the catalyst, and in particular the Pt deposition method, affects the surface site energy distribution and consequently the adsorptive properties towards H2 and CO. It was found that both H2 and CO are chemisorbed on the investigated samples. Pt/C powders exhibit higher differential heats of carbon monoxide adsorption in comparison with hydrogen adsorption. A reaction between pre-adsorbed H2 and CO from the gas phase takes place on Pt/C catalysts as a result of competitive adsorption.  相似文献   

13.
The addition of various metals to Pt-coated ceramic foam monoliths was examined for the autothermal oxidative dehydrogenation of ethane to ethylene at 900°C at contact times of 5 ms. The addition of Sn or Cu to Pt-monoliths enhanced both C2H6 conversions and C2H4 selectivities significantly, giving higher C2H4 yields. No deactivation or volatilization of the catalysts was observed. For Pt-Sn, an increase in the Sn/Pt ratio from 1/1 to 7/1 increased both the conversion and the selectivity. For Pt-Sn (Sn/Pt = 7/1) versus Pt alone the conversion increased by up to 6% and the selectivity up to 5% for an increase in optimal yield from 54.5% with Pt to 58.5% with Pt-Sn. XRD and XPS measurements showed that Pt existed in the form of PtSn and Pt3Sn alloys. The 1/1 Pt-Cu catalyst showed comparable performance, with conversion increasing by 5% and selectivity by 3%. The addition of several other metals to Pt-monoliths decreased both C2H6 conversion and C2H4 selectivity in the order, Sn>Cu>Pt alone>Ag>Mg>Ce>Ni>La> Co. For oxidative dehydrogenation ofn-butane and isobutane, Pt-Sn and Pt-Cu also showed higher conversion than Pt.This research was partially supported by NSF under Grant CTS-9311295.  相似文献   

14.
Carbon supported PtSn alloy and PtSnOx particles with nominal Pt:Sn ratios of 3:1 were prepared by a modified polyol method. High resolution transmission electron microscopy (HRTEM) and X-ray microchemical analysis were used to characterize the composition, size, distribution, and morphology of PtSn particles. The particles are predominantly single nanocrystals with diameters in the order of 2.0-3.0 nm. According to the XRD results, the lattice constant of Pt in the PtSn alloy is dilated due to Sn atoms penetrating into the Pt crystalline lattice. While for PtSnOx nanoparticles, the lattice constant of Pt only changed a little. HRTEM micrograph of PtSnOx clearly shows that the change of the spacing of Pt (1 1 1) plane is neglectable, meanwhile, SnO2 nanoparticles, characterized with the nominal 0.264 nm spacing of SnO2 (1 0 1) plane, were found in the vicinity of Pt particles. In contrast, the HRTEM micrograph of PtSn alloy shows that the spacing of Pt (1 1 1) plane extends to 0.234 nm from the original 0.226 nm. High resolution energy dispersive X-ray spectroscopy (HR-EDS) analyses show that all investigated particles in the two PtSn catalysts represent uniform Pt/Sn compositions very close to the nominal one. Cyclic voltammograms (CV) in sulfuric acid show that the hydrogen ad/desorption was inhibited on the surface of PtSn alloy compared to that on the surface of the PtSnOx catalyst. PtSnOx catalyst showed higher catalytic activity for ethanol electro-oxidation than PtSn alloy from the results of chronoamperometry (CA) analysis and the performance of direct ethanol fuel cells (DEFCs). It is deduced that the unchanged lattice parameter of Pt in the PtSnOx catalyst is favorable to ethanol adsorption and meanwhile, tin oxide in the vicinity of Pt nanoparticles could offer oxygen species conveniently to remove the CO-like species of ethanolic residues to free Pt active sites.  相似文献   

15.
The structure, surface composition and activity/selectivity for ethanol oxidation of carbon supported Pt alloy catalysts with different composition and catalyst loading, which were synthesized via the polyol-route, were investigated and characterized by microscopic/spectroscopic methods (TEM, EDX, XRD) and electrochemical (RDE, on-line DEMS) measurements under well-defined transport and diffusion conditions. The performance of the polyol-type Pt/C (20 wt.%), PtRu/C (20, 40 and 60 wt.%), and Pt3Sn/C (20 wt.%) catalysts was compared with that of commercial Pt/C, PtRu/C and Pt3Sn/C (E-Tek) catalysts. The metal particle sizes of the polyol-type catalysts are significantly smaller than those of the corresponding commercial catalysts, nevertheless both the mass specific activities and, more pronounced, the inherent, active surface area specific activities are lower than those of the commercial catalysts, which is related to the lower degree of alloy formation in the polyol-type catalysts. For all catalysts, incomplete ethanol oxidation to C2 products (acetaldehyde and acetic acid) prevails under conditions of this study, CO2 formation contributes by ≤1% for potentiostatic reaction conditions. The lower activity of the polyol-type catalysts is mainly due to the lower activity for acetaldehyde formation. Implications and further strategies for fuel cell applications are discussed.  相似文献   

16.
PtSn/Al2O3 and PtSn/Al2O3–Na catalysts display important modifications of the metallic phase with respect to Pt/Al2O3 one. In this sense, TPR and XPS results show the presence of strong interactions between Pt and Sn, with probable alloy formation, which would be responsible for the decrease of the reaction rate and the increase of the activation energy in cyclohexane dehydrogenation. Besides the experiments of cyclopentane hydrogenolysis show that the alkali metal addition to bimetallic PtSn/Al2O3 catalysts completely eliminates the hydrogenolytic ensembles, which could be due to a geometric modification of the metallic phase. These important modifications in the nature of the metallic function due to the simultaneous addition of Na and Sn to Pt/Al2O3 are responsible for the excellent catalytic performance in the n-butane dehydrogenation, thus giving high conversions, selectivities to butenes higher than 95%, and lower deactivation capacity than those corresponding to bimetallic PtSn catalysts (with different Sn contents) supported on undoped alumina. The excellent stability of PtSn/Al2O3–Na catalysts would be due to a low carbon formation during the reaction, such as it was observed from pulse experiments.  相似文献   

17.
In an exploratory approach to find improved electrocatalyst formulations binary and ternary carbon supported catalysts with the elements Pt and Ru, W, Mo or Sn, respectively, amending the choice of Pt and Pt/Ru catalysts by addition of non-Pt metal cocatalysts were manufactured by impregnation and a colloid method and tested towards their activity for anodic oxidation of H2 containing 150 ppm CO and of methanol. Membrane-electrode-assemblies with noble metal loadings of 0.4 mg cm−2 were manufactured and tested in fuel cell operation at 75°C with H2 fuel contaminated by CO and at 95°C for operation on methanol. Cocatalytic activities were found for the elements W and Mo for oxidation of H2/CO and methanol while in the case of Sn a cocatalytic activity was only found for H2/CO-oxidation. Both for oxidation of methanol and H2/CO the system Pt/Ru/W was superior to the other systems tested. The colloid method was found to be highly suitable for synthesizing polymetallic PEM catalysts.  相似文献   

18.
Direct formic acid fuel cells (DFAFC) currently employ either Pt-based or Pd-based anode catalysts for oxidation of formic acid. However, improvements are needed in either the activity of Pt-based catalysts or the stability of Pd-based catalysts. In this study, a number of carbon-supported Pt-based and Pd-based catalysts, were prepared by co-depositing PdM (M = Bi, Mo, or V) on Vulcan® XC-72 carbon black, or depositing another metal (Pb or Sn) on a Pt/C catalyst. These catalysts were systematically evaluated and compared with commercial Pd/C, PtRu/C, and Pt/C catalysts in a multi-anode DFAFC. The PtPb/C and PtSn/C catalysts were found to show significantly higher activities than the commercial Pt/C catalyst, while the PdBi/C provided higher stability than the commercial Pd/C catalyst.  相似文献   

19.
n‐hexane was reacted on two Pt–Sn/Al2O3 catalysts, one prepared by coimpregnation (T) the other by using a bimetallic PtSn complex precursor (N). Both catalysts produced isomers, methylcyclopentane fragments and benzene, the aromatic selectivity being higher on catalyst N. The hydrocarbon entities remaining after reaction were removed by hydrogen treatment. They contained methane, C2–C5 fragments (not observed on Pt, thus unique for PtSn) and benzene. The possible state and composition of chemisorbed carbonaceous entities during reactions are discussed. More hydrocarbons, including slightly more methane could be hydrogenated off from catalyst N of lower dispersion. The higher overall activity of catalyst N in the presence of more than one C per surface Pt points to its higher coke tolerance. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

20.
In this work we have studied the effect of the addition of Sn to alumina-supported Pt catalysts towards the catalytic performance in CO-PROX reaction. Monometallic Pt and Sn catalysts supported on alumina, and bimetallic Pt–Sn supported on alumina (with Pt/Sn atomic ratios of 1.92, 0.53 and 0.28) was prepared by successive impregnation, with high dispersion of the metal. The addition of Sn to Pt does not substantially increase the activity in CO-PROX at low temperatures; however, the temperature interval where the CO conversion is maximum was significantly increased. The optimum Pt/Sn atomic ratio was found to be 0.53. In a wide operation window with respect to temperature, the catalyst with optimum Pt to Sn ratio shows a maximum CO conversion of 78% for λ = 2 with constant selectivity (about 40%) and with 31%CO yield. In the presence of either CO2 or H2O the performance of Sn promoted catalyst was seen to show improved activity.  相似文献   

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