• <tr id="yyy80"></tr>
  • <sup id="yyy80"></sup>
  • <tfoot id="yyy80"><noscript id="yyy80"></noscript></tfoot>
  • 99热精品在线国产_美女午夜性视频免费_国产精品国产高清国产av_av欧美777_自拍偷自拍亚洲精品老妇_亚洲熟女精品中文字幕_www日本黄色视频网_国产精品野战在线观看 ?

    Effects of TiO2 in Pd-TiO2/C for glycerol oxidation in a direct alkaline fuel cell

    2022-05-04 05:59:36VivianeSantosPereiralioNandenhaAndrezzaRamosAlmirOliveiraNeto
    燃料化學(xué)學(xué)報(bào) 2022年4期

    Viviane Santos Pereira,Júlio Nandenha,Andrezza Ramos,Almir Oliveira Neto

    (Instituto de Pesquisas Energéticas e Nucleares-IPEN-CNEN/SP Centro de Células a Combustível e Hidrogênio-CECCO ,Cidade Universitária, S?o Paulo-SP 05508-000, Brasil)

    Abstract: The Pd-TiO2 electrocatalysts were synthesized via sodium borohydride reduction and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), cyclic voltammetry, chronoamperometry and attenuated total reflectance-Fourier transform infrared (ATR-FTIR). The X-ray diffraction experiments of the Pd-TiO2 showed peaks associated with Pd face-centered cubic (fcc) structure and peaks characteristics of TiO2 (anatase phase) with a tetragonal structure. The TEM images showed that the Pd and TiO2 nanoparticles were well distributed in the carbon support showing some clustered regions with nanoparticle sizes between 7 and 8 nm. Cyclic voltammograms showed an increase in current density values after the glycerol adsorption process. Experiments in alkaline direct glycerol fuel cells at 60 °C showed a higher power density for Pd-TiO2/C (70∶30) in comparison to the commercial Pd/C electrocatalyst indicating that the use of the TiO2 co-catalyst with Pd nanoparticles had a beneficial behavior. This effect can be attributed to the electronic effect or to the bifunctional mechanism. Molecules with high-value added glyceraldehyde, hydroxypyruvate and formate were identified as electrochemical reaction products of glycerol on all prepared electrocatalysts.

    Key words:glycerol oxidation;Pd-TiO2 electrocatalysts;in-situ ATR-FTIR;cyclic voltammetry;alkaline fuel cell

    Direct alcohol fuel cells (DAFCs) have a high energy density and are easy to handle when compared to PEMFC cells that use hydrogen (H2) as fuel. In this context, cells (DAFCs) are considered potential alternative energy sources with the possibility of application in portable equipment and electronic devices, in addition to the possible production of products with high added value[1,2].

    Glycerol fuel applied to an Alkaline Direct Glycerol Fuel Cell (ADGFC) is very attractive because it has a high energy density with a theoretical value close to 6.4 kW·h/L, it is not toxic, and is a nonflammable liquid and of low cost. It presents advantages regarding its application and use in a direct alcohol fuel cell due to the reduction of environmental impacts and the possibility of conversion into highvalue added products[3]. The main challenge of this fuel for commercialization in ADFC lies in the kinetics of the glycerol oxidation reaction, that is, the breaking the C?C bonds and completing the oxidation to CO2[4,5].

    Pt and Pd nanoparticles are commonly used as primary electrocatalysts in the anode of one ADGFC due to Pt-based electrocatalysts has a chemical stability and high catalytic activity, but it is considered a rare material in the nature and of high cost, in addition to suffering CO poisoning. The decrease in the activities of electrocatalysts during the oxidation reaction is evidenced by the formation of intense adsorbed intermediates on its surface[6]. Electrocatalysts based on Pd nanoparticles in alkaline medium for alcohol oxidation have been shown good results, these electrocatalysts also showed resistance to poisoning by intermediates adsorbed (CO) on the Pd surface.However, their contribution becomes limiting and dependent on factors such as support material,morphology and distribution[7,8].

    However, the performance of Pd increase also when combined with other metals such as Ru[9], Ni[10],Au[11], Ag[12], In[13]and Co[14]in the form of alloys,deposits or anchors. In this context, new studies with materials for the synthesis of cheaper and more efficient electrocatalysts that help to improve reaction kinetics in a direct glycerol fuel cell have been developed.

    The combination of Pd with titanium dioxide(TiO2) was studied in this work to investigate the catalytic activity and the possible production of products with high added value in the oxidation of glycerol fuel. Titanium dioxide is attractive to be used in the composition of an electrocatalyst because it has resistance to corrosion and tolerance to intermediates formed in the reaction, such as carbon monoxide (CO).TiO2can be used as a doping material on carbon support or as a co-catalyst[15?18]. Silva et al.[16]synthesized Pd/TiO2-C electrocatalysts for ethanol oxidation in an alkaline medium and showed good results due to the formation of OH species from TiO2,facilitating the oxidation of ethanol fuel, and also observed the change in thedband of Pd in this material due to the strong interaction between metal and support.

    Han et al.[17]prepared the TiO2-Au/C electrocatalyst for glycerol oxidation in an alkaline medium, and they observed an improvement in the catalytic activity as well as a change in the glycerol reaction pathway due to TiO2-Au interfaces formed during the preparation, attributing the increase of catalytic performance to TiO2by facilitating oxidation on the Au surface. Souza et al.[18]investigated the combination Pd-TiO2/C (50∶50) for methane activation in an acidic medium, observing the formation of high added value products such as methanol. They attributed the improvement in catalytic activity and stability of the materials to the presence of TiO2. The presence of TiO2also favors the adsorption of some intermediates for the methane oxidation reaction on the Pd surface,thus increasing the catalytic performance of the prepared electrocatalysts.

    In this work we present a study that aims to contribute to the understanding of the use of Pd-TiO2/C electrocatalysts with different atomic compositions(50∶50, 70∶30 and 90∶10) supported with Carbon Vulcan XC72?used in the oxidation of glycerol fuel.

    1 Synthesis, characterization and experiments

    1.1 Preparation of electrocatalysts

    Pd/C, TiO2/C and Pd-TiO2/C (50∶50, 70∶30 and 90∶10) electrocatalysts were prepared by the sodium borohydride reduction method[18,19]. The metal salt Pd(NO3)2-2H2O (Aldrich) and (TiO2-(Aldrich) were used as metallic precursors, (NaBH4-(Aldrich) as a reducing agent and Carbon Vulcan XC72?(Cabot,Corp. USA) was used as support[18]. Initially, the ions metallic were dissolved in a mixture of water with 2-propanol (50:50 volume ratio), and the Carbon Vulcan XC72?support was added in the solution. The resulting mixture was submitted to an ultrasonic probe sonicator for 10 min for homogenization. After this step,(NaBH4:metal molar ratio equal to 5∶1 was added in one step under magnetic stirring for 1 h at room temperature to reduction of metallic salts. Finally, the resulting mixtures were filtered, and the solids(electrocatalysts) washed with ultrapure water and dried at 70 °C for 2 h.

    1.2 Electrocatalysts characterization

    1.2.1 Energy-dispersive X-ray spectroscopy (EDX)

    The energy-dispersive X-ray spectroscopy analyzes were performed in an equipment containing a scanning electron microscope (SEM), with a 20 keV electron beam, model Philips XL30 equipped with an EDAX microanalyzer, model DX-4 was used for analysis. Samples were prepared with a small amount of powdered electrocatalyst over a sticky paint on the detection support. The data collected correspond to an average of four random points in each sample to obtain the real atomic compositions[20].

    1.2.2 X-ray diffraction (XRD)

    X-ray diffraction analyses were performed in a conventional diffractometer, (Rigaku, model Miniflex II) with a CuKα radiation source (λ= 0.15406 nm).The diffractograms were obtained in the range scanning angle 2θfrom 20° to 90° with a step size of 0.05° and scan time of 2 s per step[18]. To carry out these experiments, a small amount of electrocatalyst powder was compacted in a glass support with the aid of silicone grease, which was introduced into the diffractometer[21].

    1.2.3 Transmission electron microscopy (TEM)

    Transmission electron microscopy analyses were performed to estimate morphology and nanoparticles distribution of the electrocatalysts on the carbon support, using JEOL transmission electron microscopy(JEM-2100) operated at 200 kV[20,21]. The samples were prepared from the suspension of the electrocatalyst in isopropyl alcohol, undergoing homogenization in an ultrasound system. Subsequently, an aliquot of the sample was placed on a copper grid of 0.3 cm diameter containing a carbon film. Mean nanoparticle sizes were digitally measured by counting about 150 nanoparticles in different regions of each sample to construct nanoparticle distribution histogram and calculate mean nanoparticle size.

    1.2.4 Cyclic voltammetry (CV) and chronoamperometry (CA)

    Cyclic voltammetry and chronoamperometry measurements were performed at room temperature using a potentiostat/galvanostat (Autolab PGSTAT 302N, Metrohm). These studies were carried out using working electrodes (geometric area of 0.0707 cm2)prepared by the ultra-thin porous coating technique, the reference electrode was an Ag/AgCl (3.0 mol/L KCl)and the counter electrode was a Pt plate. The electrochemical measurements were performed in the presence of 1.0 mol/L KOH or 1.0 mol/L glycerol in 1.0 mol/L of KOH solutions saturated with N2. The cyclic voltammetry experiments were done at a scan rate of 10 mV/s for the potential range from ?0.85 to 0.2 V versus Ag/AgCl[22]. The chronoamperometry analyses were carried out keeping the same setup of cyclic voltammetry using 1.0 mol/L glycerol in 1.0 mol/L KOH solution at ?0.35 V versus Ag/AgCl for 1800 s[22].

    1.2.5 Attenuated total reflection-Fourier transform infrared (ATR-FTIR)

    The ATR-FT-IR measurements were performed on a Nicolet?6700 FT-IR spectrometer equipped with an MCT detector cooled with liquid N2, ATR accessory(MIRacle with a ZnSe Crystal Plate Pike?) installed is coupled to the spectrometer, to identify the products formed during the electrochemical oxidation of glycerol in alkaline medium in different potentials.

    1.2.6 Alkaline direct glycerol fuel cell test

    Alkaline Direct Glycerol Fuel Cell Tests were carried out using Pd/C, TiO2and Pd-TiO2/C electrocatalysts as anodes and Pt/C electrocatalysts as cathodes in a single fuel cell with an area of 5 cm?2. For Alkaline direct glycerol fuel cell studies it was used the carbon-cloth treated with Teflon and with the presence of Carbon Vulcan XC72?as a gas diffusion layer, and a Nafion?117 membrane as electrolyte. The electrodes(anode and cathode) were hot pressed on both sides of a Nafion?117 membrane at 125 °C for 10 min under a pressure of 225 kgf/cm2[23]. The prepared electrodes contain Pd 1 mg/cm2at the anode and Pt 1 mg/cm2at the cathode. The temperature was set to 60 °C for the fuel cell and 85 °C for the oxygen humidifier. 2 mol/L glycerol in 2 mol/L KOH aqueous solution was delivered at 1 mL/min, and the oxygen flow was regulated to 150 mL/min[5]. Polarization curves were obtained using a potentiostat/galvanostat (Autolab, model PGSTAT 302 N).

    2 Results and discussion

    The results of the nominal atomic ratios and atomic ratios obtained by EDX for the synthesized Pd-TiO2/C (50∶50, 70∶30 and 90∶10) electrocatalysts are presented in Table 1.

    For Pd-TiO2/C binary electrocatalysts synthesized with different atomic proportions, the EDX analyses revealed that the atomic ratios (Pd:TiO2) obtained were similar to the nominal atomic ratios (Table 1),therefore, these results indicated that the sodium borohydride reduction method is efficient for the production of the proposed electrocatalysts.

    Table 1 Nominal atomic ratios and atomic ratios obtained by EDX of the Pd-TiO2/C (50∶50, 70∶30 and 90∶10)electrocatalysts synthesized by the sodium borohydride reduction method

    The X-ray diffractograms of the as-synthesized electrocatalysts are shown in the Figure 1. All diffractograms, showed the presence of a peak centered at about 2θ≈ 24° associated with the (004) plane of the carbon support. The Pd/C and Pd-TiO2/C electrocatalysts also presented four peaks at about 2θ≈ 40°, 47°, 68°and 82° associated, respectively, to the (111), (200),(220) and (311) planes of face-centered cubic (fcc)structure of Pd or Pd alloys (JCPDF#89-4897)[20,24?26].Pd-TiO2/C and TiO2showed peaks at approximately 2θ≈ 25°, 37°, 38°, 39°, 48°, 54°, 69° and 70°, associated with (101), (103), (004), (112), (200), (105), (116) and(220) crystalline planes of the tetragonal structure(JCPDF#2-387)[20,24], which were characteristics of titanium oxide (TiO2-anatase phase) as already evidenced by Silva et al. and De Souza et al.[16,18].

    Figure 1 X-ray diffractograms of the Pd/C, TiO2/C, Pd-TiO2/C(50∶50, 70∶30 and 90∶10) electrocatalysts synthesized by the sodium borohydride reduction method

    The mean crystallite sizes of the studied electrocatalysts were from 2.0 to 4.3 nm. As seen in Figure 1, the results did not show peak detachment for smaller or larger angles, indicating that there was no formation of metallic alloys in the composition of the synthesized electrocatalysts. The micrographs obtained by transmission electron microscopy analysis and its histograms are shown in Figure 2.

    Figure 2 Micrographs and the size distribution of nanoparticles obtained by transmission electron microscopy: (a) Pd/C, (b) TiO2/C,(c) Pd-TiO2/C (50∶50), (d) Pd-TiO2/C (70∶30), (e) Pd-TiO2/C (90∶10)

    The Pd/C and TiO2/C electrocatalysts had mean nanoparticle sizes of 7.2 and 8.0 nm and standard deviations of 1.7 and 2.2 nm. The Pd-TiO2/C (50∶50),Pd-TiO2/C (70∶30) and Pd-TiO2/C (90∶10) binary electrocatalysts, presented mean nanoparticle sizes of 7.0, 7.0 and 8.0 nm, respectively, with standard deviations of 2.1, 1.5 and 1.0 nm. All micrographs obtained showed some agglomeration regions of the nanoparticles on the carbon support.

    All electrocatalysts studied by electrochemical measurements were normalized by milligram of palladium (Pd) considering that the adsorption/desorption process of the studied fuels is directly related to the palladium (Pd) sites at room temperature.The cyclic voltammograms were made in the absence of glycerol (Figure 3). The cyclic voltammograms of Pd/C, Pd-TiO2/C (50∶50, 70∶30 and 90∶10) exhibited a well-defined hydrogen adsorption/desorption region at(?0.85 to ?0.5 V), (Figure 3). In these experiments a shift of the peak position to more negative potentials at about?0.7 V in the adsorption/desorption region (anodic scanning) of hydrogen for Pd-TiO2/C (50∶50) can also be observed when compared to the Pd/C, Pd-TiO2/C(70∶30) and Pd-TiO2/C (90∶10) electrocatalysts,indicating a possible electronic modification of palladium atoms by the neighboring titanium dioxide atoms. Han et al.[15]prepared the TiO2-Ni composition for glycerol oxidation. Cyclic voltammetry studies showed the presence of hydroxyl formation peaks on the material surface, originating from TiO2electron orbitals.

    Figure 3 Cyclic voltammograms of Pd/C, TiO2/C, Pd-TiO2/C(50∶50, 70∶30 and 90∶10) electrocatalysts in a 1 mol/L KOH solution at room temperature at a scan rate of 10 mV/s

    In Figure 3, an increase in the current values in the electric double layer at about ?0.5 to 0.0 V was observed in the Pd-TiO2/C (50∶50) and Pd-TiO2/C(70∶30) binary electrocatalysts in comparison with Pd/C, indicating the formation of Pd oxides in the anodic scan, possibly due to a greater amount of adsorbed oxygen species (OHads)[23]. Grdén et al.[27]reported that the choice of material composition for the formation of an electrocatalyst can lead to an increase in adsorbed oxygen species on its surface, playing a decisive role in the hydrogen adsorption/desorption process.

    In Figure 4, the onset of glycerol oxidation was observed at more negative potentials (?0.4 V) for Pd-TiO2/C (70∶30) with a higher current value with oxidation peak at 14.91 mA/cm2when compared to Pd-TiO2/C (50∶50) and Pd-TiO2/C (90∶10) binary electrocatalysts, which had oxidation onset at less negative potentials at ?0.36 V with oxidation peaks at 9.37 and 4.88 mA/cm2, respectively. The Pd/C and TiO2/C electrocatalysts started the glycerol oxidation at about ?0.2 V with oxidation peaks at around 1.08 and 0.55 mA/cm2respectively (Figure 4). Geraldes et al.[5]investigated the electrochemical oxidation of glycerol in alkaline electrolyte using the PdAu/C, PdSn/C and PdAuSn/C electrocatalysts, and obtained good results,in which its performance was attributed to the bifunctional mechanism, where Au and Sn provide OHspecies favoring the oxidation of intermediates adsorbed on the Pd surface.

    Figure 4 Cyclic voltammograms of glycerol electro-oxidation on Pd/C, TiO2, Pd-TiO2/C (50∶50, 70∶30 and 90∶10)electrocatalysts using 1.0 mol/L glycerol in 1.0 mol/L KOH electrolyte at room temperature with a scan rate of 10 mV/s

    Ottoni et al.[23]studied the Pd/C, Pd/ITO and Pd/CITO combinations in the oxidation of glycerol in an alkaline medium and highlighted the Pd/C-ITO material that presented the best electrocatalytic performance in relation to the Pd/C that obtained inferior performance. The authors associated the best results with the bifunctional mechanism and electronic effect.

    In the present work it was possible to notice that the metallic material Pd and TiO2when acting alone in the oxidation of glycerol do not present high current values, the opposite was observed when combined in different atomic ratios and this response could be attributed to synergy between the materials as well as to events such as the bifunctional mechanism or electronic effect.

    The superior catalytic activity of Pd-TiO2/C(70:30) electrocatalyst (Figure 4) could be attributed to the smaller mean nanoparticle sizes as observed in the transmission electron microscopy (TEM) images, as the primary factor for the catalytic activities of reactions in an electrocatalyst take place on its surface,so the smaller nanoparticle size can significantly increase the catalytic activity process. Yanya et al.[4]described that the smaller size of PdAu nanoparticles for glycerol oxidation in an alkaline medium contributed to the improvement of its electrocatalytic activity. The chronoamperometries obtained are shown in Figure 5.

    Figure 5 Current versus time curves at ?0.35 V in a 1.0 mol/L KOH solution in the presence of 1.0 mol/L glycerol for Pd/C,TiO2, Pd-TiO2/C (50∶50, 70∶30 and 90∶10) electrocatalysts at room temperature at a scan rate of 10 mV/s

    The current values obtained for Pd-TiO2/C(50∶50) and Pd-TiO2/C (70∶30) electrocatalysts were highest being almost twice higher than those of standard Pd/C and TiO2/C (Figure 5). For the Pd-TiO2/C (70∶30) electrocatalyst there is a slight decay over time compared to Pd-TiO2/C (50∶50). This behavior might be associated with the presence of adsorbed intermediates on the surface of this electrocatalyst in the glycerol oxidation process, as already observed in the literature[14,28]. However, the Pd-TiO2/C (70∶30) and Pd-TiO2/C (50∶50) compositions tend to remain active indicating that these stipulated atomic compositions were the most appropriate for the oxidation of glycerol as they presented lower potentials at the beginning of the glycerol oxidation process and higher current values, as seen in Figure 4 and Figure 5.

    In Figure 6, the Pd-TiO2/C (50∶50, 70∶30 and 90∶10) electrocatalysts presented open-circuit voltage(OCV) values in 798, 817, 875 mV, respectively,whereas the Pd/C and TiO2/C electrocatalysts presented the OCV values of 674 and 713 mV (Figure 6A-(I)).The maximum power density values were 12.4, 12.5 and 7.9 mW/cm2for the Pd-TiO2/C electrocatalysts(50∶50, 70∶30 and 90∶10), 3.70 and 2,25 mW/cm2for the Pd/C and TiO2/C electrocatalysts, respectively(Figure 6A-(I)).

    Figure 6 Polarization (A-(I)) curves and power density (A-(II))in a 5 cm2 alkaline direct glycerol fuel cell (ADGFC) at 60 °C,using Pd/C, TiO2/C and Pd-TiO2/C electrocatalysts with different atomic proportions fed with 2.0 mol/L glycerol in a 2.0 mol/L KOH solution and oxygen flux was set to 150 mL min at 85 °C

    The Pd-TiO2/C (70∶30) combination obtained the best maximum power density activity and open-circuit voltage value, confirming the performance observed in the cyclic voltammetry and chronoamperometry experiments (Figure 4 and Figure 5), probably due to the higher formation of oxygenated species for the oxidation of COadson the Pd surface[23]. Lower values of maximum power density and open-circuit voltage were observed for Pd/C, TiO2/C when compared to PdTiO2/C (50∶50, 70∶30 and 90∶10), possibly due to resistivities of its electrodes that can hinder glycerol diffusion through the catalytic layer. Han et al.[17]studied the Au-TiO2combination and reported that the improvement of the catalytic system might be associated with the role of TiO2in facilitating the glycerol oxidation on the gold surface. This response was also observed in this work.

    The ART-FTIR spectra of Pd/C, TiO2/C, Pd-TiO2/C (50∶50, 70∶30 and 90∶10) are shown in Figure 7 and the interpretation of the absorption bands for each molecule formed from the partial glycerol electrooxidation reaction was based on the comparison between standard FT-IR by considering the authors Winiwarter et al.[29]and the works of Gomes et al.[30]and Zalineeva et al.[31].

    Figure 7 FT-IR spectra obtained from products collected at different potentials in increments of 100 mV in alkaline direct glycerol fuel cell (ADGFC) experiments using Pd/C, TiO2/C, Pd-TiO2/C (50∶50, 70∶30 and 90∶10) electrocatalysts

    The Pd/C electrocatalyst showed efficiency in the glycerol oxidation, and led to the formation of the formate located at 1225 cm?1present in all potentials and was more intense at 0.69 V. The presence of the hydroxypyruvate band in 1355 cm?1was observed at all potentials and was more intense at 0.59 and 0.69 V respectively[30]. The mesoxalate that would occur from the hidroxypyruvate oxidation was not observed in the samples obtained (in the glycerol oxidation using Pd/C,TiO2/C or the Pd-TiO2/C (50∶50, 70∶30 and 90∶10)binary. Thus, the intermediate molecules of the partial glycerol electro-oxidation reaction were formed and consumed simultaneously.

    Glycerate was observed at 1377 cm?1at all potentials, and this was less intense at 0.19 and 0.29 V at Pd/C. The carbonate and carboxylate were located at 1405 and 1575 cm?1respectively and were more intense from 0.59 to 0.69 V[30,31]. The intensities of the bands corresponding to the glycerol electro-oxidation products of the TiO2/C electrocatalyst are significantly lower than those related to the glycerol electrooxidation reaction in Pd/C electrocatalysts and those with higher proportions of Pd such as Pd-TiO2/C (with 50%, 70% and 90 % of Pd).

    In the FT-IR spectra of all electrocatalysts, no peaks close to 2050 cm?1were observed, this fact can be attributed to the stretching vibration of CO species linearly bound to the surface of the electrocatalyst.However, implying that the reaction in these electrocatalysts does not include the CO formation as an intermediate[32,33]. Confirming that there is no total oxidation in the potential range observed for these electrocatalysts. According to the electrochemical results obtained, the PdTiO2/C (50∶50) and PdTiO2/C(70∶30) electrocatalysts were more promising than Pd/C, TiO2/C and Pd-TiO2(90∶10). In the PdTiO2/C electrocatalyst (50∶50) the bands of the reaction products formed were more evident from 0.30 V.Moreover, in the PdTiO2/C (70∶30) electrocatalyst the bands that tended to increase together with the value of potential were observed.

    Table 2 shows the products formed with the different electrocatalysts studied. According to the electrochemical results obtained, the Pd-TiO2(50∶50)and Pd-TiO2(70∶30) electrocatalysts were more promising than Pd/C, TiO2/C and Pd-TiO2(90∶10),with respect to the rate of reaction. However, for the Pd-TiO2(50∶50) electrocatalyst, the bands of the reaction products formed were more evident from?0.30 V, while for the Pd-TiO2(70∶30) electrocatalyst,varying intensities along the potentials were observed.

    Table 2 Molecules formation in the partial electro-oxidation reaction of glycerol at different potentials using combined Pd/C and TiO2/C electrocatalysts

    3 Conclusions

    The sodium borohydride reduction method was an efficient process to produce Pd/C, TiO2/C and Pd-TiO2/C electrocatalysts for glycerol oxidation because atomic ratios EDX (%) result showed that the amount of Pd and TiO2in the synthesized electrocatalysts is close to those nominal atomic ratios (%), as expected.All Pd-TiO2/C electrocatalysts were promising for the glycerol oxidation in comparison with Pd/C and TiO2/C. Pd-TiO2/C obtained showed the presence of segregated face-centered cubic (fcc) structure Pd-rich and that also showed peaks associated with the tetragonal structure characteristics of titanium oxide(TiO2-anatase phase). The ATR-FTIR results showed the complexity of glycerol oxidation with the formation of different oxidation products. The electrochemical measurements and the experiments in a single DFAFC showed that Pd-TiO2/C (50∶50), Pd-TiO2/C (70∶30)and Pd-TiO2/C (90∶10) exhibited superior performance for glycerol electrochemical oxidation than Pd/C electrocatalyst. The highest catalytic activity of Pd-TiO2/C (70∶30) electrocatalyst could be attributed to the synergy between the constituents of the electrocatalyst (metallic Pd and TiO2). Further work still need to be done in order to investigate the electrocatalyst surface and to elucidate the mechanism of glycerol electrochemical oxidation using these electrocatalysts, as well as to understand the electronic effect that TiO2causes in Pd atomic structure.

    99riav亚洲国产免费| 精品福利观看| 人人澡人人妻人| 久久久精品国产亚洲av高清涩受| 啪啪无遮挡十八禁网站| 99在线人妻在线中文字幕 | 国产精品自产拍在线观看55亚洲 | 亚洲精品乱久久久久久| 午夜精品久久久久久毛片777| 久久中文字幕一级| 久热这里只有精品99| 欧美+亚洲+日韩+国产| 老司机深夜福利视频在线观看| 一级毛片女人18水好多| 精品久久久久久电影网| 午夜福利免费观看在线| 亚洲国产精品合色在线| 国产日韩一区二区三区精品不卡| 国产麻豆69| 国产一区二区三区综合在线观看| 亚洲熟女毛片儿| 窝窝影院91人妻| 久久久久视频综合| 热99re8久久精品国产| 午夜亚洲福利在线播放| 日韩三级视频一区二区三区| 80岁老熟妇乱子伦牲交| 一进一出抽搐gif免费好疼 | 精品高清国产在线一区| 黑人猛操日本美女一级片| 久久久精品国产亚洲av高清涩受| 超色免费av| 精品国产一区二区三区久久久樱花| 啦啦啦 在线观看视频| 久久精品aⅴ一区二区三区四区| 老熟女久久久| 女同久久另类99精品国产91| 亚洲欧美日韩高清在线视频| 免费久久久久久久精品成人欧美视频| 一级片'在线观看视频| 免费在线观看黄色视频的| 一区二区三区精品91| 亚洲精华国产精华精| 极品教师在线免费播放| 人人妻人人澡人人爽人人夜夜| 午夜福利乱码中文字幕| 乱人伦中国视频| 久久久久久久国产电影| 亚洲精品一卡2卡三卡4卡5卡| 高清欧美精品videossex| 日日摸夜夜添夜夜添小说| 老司机午夜福利在线观看视频| 老司机午夜十八禁免费视频| 在线观看免费午夜福利视频| 久久香蕉激情| 亚洲五月婷婷丁香| 十八禁人妻一区二区| 一级片免费观看大全| 久久中文字幕人妻熟女| 国产淫语在线视频| 成年版毛片免费区| 亚洲午夜理论影院| 最新在线观看一区二区三区| 久久这里只有精品19| 麻豆国产av国片精品| 18在线观看网站| 成年人黄色毛片网站| 中文欧美无线码| 午夜精品久久久久久毛片777| 亚洲色图 男人天堂 中文字幕| 亚洲av熟女| 国产男女超爽视频在线观看| 国产精品九九99| 一二三四社区在线视频社区8| 久久天堂一区二区三区四区| 精品亚洲成国产av| 亚洲国产看品久久| 一进一出好大好爽视频| 国产真人三级小视频在线观看| 国产不卡一卡二| 亚洲成人免费av在线播放| 一进一出抽搐gif免费好疼 | 国产成+人综合+亚洲专区| 黄色怎么调成土黄色| 免费av中文字幕在线| 精品欧美一区二区三区在线| 久久草成人影院| 亚洲精品乱久久久久久| 婷婷丁香在线五月| 91麻豆av在线| 中文字幕最新亚洲高清| 欧美丝袜亚洲另类 | 狠狠婷婷综合久久久久久88av| 80岁老熟妇乱子伦牲交| 婷婷精品国产亚洲av在线 | 99精品久久久久人妻精品| 国产精品美女特级片免费视频播放器 | 免费看a级黄色片| 亚洲美女黄片视频| 新久久久久国产一级毛片| 巨乳人妻的诱惑在线观看| 亚洲精品美女久久av网站| 国产av精品麻豆| 在线天堂中文资源库| 国产精品二区激情视频| 90打野战视频偷拍视频| 亚洲欧美一区二区三区黑人| 国产黄色免费在线视频| 亚洲精品中文字幕一二三四区| 一夜夜www| a级毛片在线看网站| 久久久久久久精品吃奶| 在线观看午夜福利视频| 欧美乱妇无乱码| 国产精品偷伦视频观看了| 极品教师在线免费播放| 国产精品自产拍在线观看55亚洲 | 黑人欧美特级aaaaaa片| 精品第一国产精品| 亚洲专区字幕在线| 亚洲色图av天堂| 国产亚洲一区二区精品| 国产视频一区二区在线看| 在线观看www视频免费| 国产欧美日韩一区二区三区在线| 天天躁夜夜躁狠狠躁躁| 精品亚洲成a人片在线观看| 十八禁高潮呻吟视频| 久久精品国产a三级三级三级| videos熟女内射| 亚洲国产精品sss在线观看 | 国产成人av激情在线播放| 亚洲在线自拍视频| 亚洲精品av麻豆狂野| 丁香六月欧美| 亚洲一区二区三区不卡视频| 看黄色毛片网站| 91在线观看av| 国产免费男女视频| 一边摸一边做爽爽视频免费| 国产亚洲精品久久久久久毛片 | 丝袜美腿诱惑在线| 男女之事视频高清在线观看| 99国产综合亚洲精品| 日本a在线网址| 久久亚洲真实| 热99re8久久精品国产| 99久久综合精品五月天人人| 久久ye,这里只有精品| 一区二区三区国产精品乱码| 好看av亚洲va欧美ⅴa在| 又黄又爽又免费观看的视频| 精品国产亚洲在线| 亚洲美女黄片视频| 国产精品久久久av美女十八| 久久精品aⅴ一区二区三区四区| 人人妻人人爽人人添夜夜欢视频| 成年人免费黄色播放视频| 天堂中文最新版在线下载| 久久精品亚洲av国产电影网| 久久久国产成人免费| 黄色丝袜av网址大全| netflix在线观看网站| 激情在线观看视频在线高清 | 亚洲成人国产一区在线观看| 中文字幕另类日韩欧美亚洲嫩草| 亚洲一卡2卡3卡4卡5卡精品中文| 成年女人毛片免费观看观看9 | 国产无遮挡羞羞视频在线观看| 国产亚洲精品第一综合不卡| 欧美激情 高清一区二区三区| 黄色视频不卡| 亚洲九九香蕉| 国产av又大| 精品午夜福利视频在线观看一区| 一级毛片女人18水好多| 亚洲国产精品合色在线| 好男人电影高清在线观看| 精品一品国产午夜福利视频| 黄色视频不卡| 18在线观看网站| 在线av久久热| 精品久久久久久久久久免费视频 | 久久久久久久精品吃奶| 欧美激情高清一区二区三区| 黑丝袜美女国产一区| 亚洲aⅴ乱码一区二区在线播放 | 一进一出抽搐gif免费好疼 | videos熟女内射| 国产91精品成人一区二区三区| 99精品欧美一区二区三区四区| 精品国产乱码久久久久久男人| 国产成人影院久久av| av福利片在线| 成人18禁高潮啪啪吃奶动态图| 久久精品国产综合久久久| 在线观看免费视频日本深夜| 99国产极品粉嫩在线观看| 国产免费av片在线观看野外av| 天堂√8在线中文| 狠狠婷婷综合久久久久久88av| 超色免费av| 免费久久久久久久精品成人欧美视频| 欧美最黄视频在线播放免费 | 免费观看a级毛片全部| 日本vs欧美在线观看视频| √禁漫天堂资源中文www| 一级毛片高清免费大全| 国产精品98久久久久久宅男小说| 99久久人妻综合| 久久久久精品人妻al黑| 日本a在线网址| 如日韩欧美国产精品一区二区三区| 国产精品秋霞免费鲁丝片| 久久午夜综合久久蜜桃| 亚洲在线自拍视频| 成人永久免费在线观看视频| 欧美性长视频在线观看| 热re99久久精品国产66热6| avwww免费| 免费高清在线观看日韩| 亚洲五月天丁香| 亚洲欧美激情综合另类| 欧美中文综合在线视频| 免费观看精品视频网站| 一边摸一边抽搐一进一出视频| 午夜精品国产一区二区电影| 国产一区在线观看成人免费| 99在线人妻在线中文字幕 | 亚洲精品久久午夜乱码| 在线十欧美十亚洲十日本专区| 久久久久久久国产电影| 欧美黑人欧美精品刺激| 18禁美女被吸乳视频| 在线观看免费午夜福利视频| 欧美国产精品一级二级三级| 99久久99久久久精品蜜桃| 国产亚洲一区二区精品| 亚洲视频免费观看视频| 久久中文字幕一级| 波多野结衣一区麻豆| 欧洲精品卡2卡3卡4卡5卡区| 又黄又粗又硬又大视频| 国产精品综合久久久久久久免费 | 亚洲av熟女| 美女 人体艺术 gogo| 亚洲欧洲精品一区二区精品久久久| 亚洲av成人一区二区三| 国产无遮挡羞羞视频在线观看| av在线播放免费不卡| 国产精品.久久久| 久久久久久久精品吃奶| 无人区码免费观看不卡| 国产aⅴ精品一区二区三区波| 手机成人av网站| 久久精品国产a三级三级三级| 亚洲熟妇熟女久久| 黄片大片在线免费观看| 男女高潮啪啪啪动态图| 亚洲一区二区三区不卡视频| 悠悠久久av| 99国产精品免费福利视频| 欧美日韩亚洲综合一区二区三区_| 后天国语完整版免费观看| 国产精品免费大片| 两性午夜刺激爽爽歪歪视频在线观看 | 亚洲久久久国产精品| 一区在线观看完整版| 人人澡人人妻人| 久久婷婷成人综合色麻豆| 久久天堂一区二区三区四区| 精品国产乱码久久久久久男人| 99久久国产精品久久久| 精品少妇久久久久久888优播| 国产亚洲av高清不卡| 欧美老熟妇乱子伦牲交| 国产精品久久视频播放| 777米奇影视久久| 天天躁日日躁夜夜躁夜夜| av线在线观看网站| 久久精品人人爽人人爽视色| 欧美日韩一级在线毛片| 看免费av毛片| 老司机靠b影院| 亚洲男人天堂网一区| 青草久久国产| 91老司机精品| 老汉色∧v一级毛片| 欧美老熟妇乱子伦牲交| 国产精品99久久99久久久不卡| 老熟女久久久| 国产精品自产拍在线观看55亚洲 | 国产精品1区2区在线观看. | 露出奶头的视频| 久久这里只有精品19| 免费在线观看日本一区| 久久久精品区二区三区| 亚洲成人国产一区在线观看| 在线观看午夜福利视频| 高清在线国产一区| 国产精品1区2区在线观看. | 母亲3免费完整高清在线观看| 精品久久蜜臀av无| 欧美日韩国产mv在线观看视频| 91字幕亚洲| 午夜福利在线免费观看网站| 免费在线观看亚洲国产| 91老司机精品| 9191精品国产免费久久| 欧美+亚洲+日韩+国产| 99国产综合亚洲精品| bbb黄色大片| 久久热在线av| 侵犯人妻中文字幕一二三四区| 日韩中文字幕欧美一区二区| 日韩 欧美 亚洲 中文字幕| 精品福利永久在线观看| 久久国产精品人妻蜜桃| 丰满饥渴人妻一区二区三| 黄色女人牲交| 精品免费久久久久久久清纯 | 天堂俺去俺来也www色官网| 天天躁狠狠躁夜夜躁狠狠躁| 欧美激情高清一区二区三区| 精品无人区乱码1区二区| 国产成人精品久久二区二区免费| 精品电影一区二区在线| 亚洲av日韩精品久久久久久密| 亚洲人成伊人成综合网2020| 在线国产一区二区在线| 老熟女久久久| 久久人妻福利社区极品人妻图片| 亚洲欧美激情综合另类| 亚洲国产欧美网| tube8黄色片| 在线看a的网站| 欧美一级毛片孕妇| 亚洲国产精品合色在线| 美女午夜性视频免费| 色精品久久人妻99蜜桃| 国产精品一区二区在线不卡| 亚洲中文字幕日韩| 欧美老熟妇乱子伦牲交| 又大又爽又粗| 亚洲在线自拍视频| 18禁观看日本| 国产精品自产拍在线观看55亚洲 | 国产乱人伦免费视频| 成年动漫av网址| 高清毛片免费观看视频网站 | 亚洲av欧美aⅴ国产| 国产激情久久老熟女| 777久久人妻少妇嫩草av网站| 国产av一区二区精品久久| 最近最新免费中文字幕在线| 国产精品一区二区在线不卡| 天堂俺去俺来也www色官网| 捣出白浆h1v1| 精品久久久久久电影网| 午夜91福利影院| 国产不卡一卡二| 在线观看午夜福利视频| 国产日韩一区二区三区精品不卡| 黄网站色视频无遮挡免费观看| 捣出白浆h1v1| 国产成人一区二区三区免费视频网站| 在线观看舔阴道视频| 久久精品熟女亚洲av麻豆精品| 亚洲一区二区三区欧美精品| 人妻丰满熟妇av一区二区三区 | 在线永久观看黄色视频| 亚洲人成电影观看| 99国产精品99久久久久| 国产精品久久久人人做人人爽| 国产成人av教育| 香蕉久久夜色| 精品人妻在线不人妻| 99久久国产精品久久久| 不卡av一区二区三区| 久久精品aⅴ一区二区三区四区| 男人操女人黄网站| 中文字幕高清在线视频| 久久国产乱子伦精品免费另类| 久久久久久久精品吃奶| 最近最新中文字幕大全电影3 | 亚洲中文日韩欧美视频| 亚洲国产毛片av蜜桃av| 母亲3免费完整高清在线观看| 淫妇啪啪啪对白视频| 色在线成人网| 亚洲av日韩在线播放| av国产精品久久久久影院| 一级a爱片免费观看的视频| 99riav亚洲国产免费| 精品久久久久久久久久免费视频 | 中出人妻视频一区二区| 亚洲精品国产区一区二| 欧美日韩乱码在线| 国产人伦9x9x在线观看| 久久人人97超碰香蕉20202| 人成视频在线观看免费观看| 丰满迷人的少妇在线观看| 老熟女久久久| 男女下面插进去视频免费观看| 久久国产精品人妻蜜桃| 嫩草影视91久久| 久久精品国产亚洲av高清一级| √禁漫天堂资源中文www| 女人被躁到高潮嗷嗷叫费观| 亚洲av日韩在线播放| 欧美久久黑人一区二区| av中文乱码字幕在线| 中国美女看黄片| 亚洲欧美一区二区三区久久| 巨乳人妻的诱惑在线观看| 青草久久国产| 精品国产国语对白av| 免费不卡黄色视频| 9热在线视频观看99| 天堂动漫精品| 精品久久久久久电影网| 国产精品1区2区在线观看. | 日韩精品免费视频一区二区三区| 麻豆av在线久日| 一级毛片高清免费大全| av在线播放免费不卡| 亚洲色图 男人天堂 中文字幕| 中文字幕av电影在线播放| 精品一区二区三卡| 人人妻人人澡人人看| 国产精品国产高清国产av | av一本久久久久| 少妇粗大呻吟视频| 69av精品久久久久久| 久久 成人 亚洲| 国产精品免费一区二区三区在线 | 亚洲中文日韩欧美视频| av视频免费观看在线观看| 操美女的视频在线观看| 黄网站色视频无遮挡免费观看| 91av网站免费观看| 夜夜躁狠狠躁天天躁| 亚洲精品在线观看二区| 国产黄色免费在线视频| 色综合婷婷激情| 成人国语在线视频| 亚洲一卡2卡3卡4卡5卡精品中文| 欧美精品啪啪一区二区三区| 天堂√8在线中文| 日本一区二区免费在线视频| 亚洲欧美日韩另类电影网站| 国产午夜精品久久久久久| 国产男女内射视频| 美女视频免费永久观看网站| 男女免费视频国产| 淫妇啪啪啪对白视频| 亚洲国产毛片av蜜桃av| tocl精华| 亚洲国产精品合色在线| 亚洲精品粉嫩美女一区| 精品欧美一区二区三区在线| 老汉色∧v一级毛片| 久久久久久久久久久久大奶| 精品国产乱子伦一区二区三区| 亚洲精品在线观看二区| 最新的欧美精品一区二区| 在线观看免费高清a一片| 亚洲视频免费观看视频| 亚洲人成伊人成综合网2020| 少妇 在线观看| 免费高清在线观看日韩| 在线播放国产精品三级| 纯流量卡能插随身wifi吗| 国产一区二区激情短视频| 成人18禁在线播放| 日本五十路高清| 欧美精品一区二区免费开放| 国产精品乱码一区二三区的特点 | 精品少妇久久久久久888优播| 免费看a级黄色片| 久久天躁狠狠躁夜夜2o2o| 亚洲av片天天在线观看| 亚洲,欧美精品.| 久久久久国产一级毛片高清牌| 999精品在线视频| 一边摸一边抽搐一进一小说 | 在线天堂中文资源库| 成熟少妇高潮喷水视频| 亚洲专区中文字幕在线| 中国美女看黄片| 女性被躁到高潮视频| 国产精品九九99| xxx96com| 久久亚洲精品不卡| 欧美丝袜亚洲另类 | 狂野欧美激情性xxxx| 亚洲国产欧美日韩在线播放| 99riav亚洲国产免费| 欧美不卡视频在线免费观看 | 曰老女人黄片| 一个人免费在线观看的高清视频| 两个人看的免费小视频| 国产在线观看jvid| 国产精品秋霞免费鲁丝片| 亚洲熟女毛片儿| 亚洲一码二码三码区别大吗| 国产成人av激情在线播放| 曰老女人黄片| 成在线人永久免费视频| 制服人妻中文乱码| 午夜福利欧美成人| 黄色片一级片一级黄色片| 一级黄色大片毛片| 国产伦人伦偷精品视频| 久久国产亚洲av麻豆专区| 人妻一区二区av| 久久久久久亚洲精品国产蜜桃av| 亚洲中文字幕日韩| 这个男人来自地球电影免费观看| 韩国av一区二区三区四区| 亚洲,欧美精品.| 国产国语露脸激情在线看| 亚洲成人免费电影在线观看| 久久亚洲真实| 久久国产亚洲av麻豆专区| www.999成人在线观看| 最新美女视频免费是黄的| 国产精品久久久av美女十八| 国产欧美日韩综合在线一区二区| 女同久久另类99精品国产91| 久久精品国产亚洲av高清一级| 黑人操中国人逼视频| 天堂√8在线中文| 久久午夜综合久久蜜桃| 中文字幕人妻丝袜一区二区| 久久精品国产99精品国产亚洲性色 | 色综合婷婷激情| 亚洲精品美女久久av网站| 久久热在线av| 在线永久观看黄色视频| 国产成人啪精品午夜网站| 午夜影院日韩av| 99热网站在线观看| 国产男靠女视频免费网站| 99精品久久久久人妻精品| 中文亚洲av片在线观看爽 | 人人澡人人妻人| 国产91精品成人一区二区三区| 欧洲精品卡2卡3卡4卡5卡区| 女人高潮潮喷娇喘18禁视频| 久久这里只有精品19| 动漫黄色视频在线观看| a在线观看视频网站| 手机成人av网站| 久久中文字幕一级| 9191精品国产免费久久| 国产欧美亚洲国产| 少妇猛男粗大的猛烈进出视频| av有码第一页| 一区二区三区国产精品乱码| 久久久水蜜桃国产精品网| 黑人欧美特级aaaaaa片| 国产真人三级小视频在线观看| 最新在线观看一区二区三区| 女人高潮潮喷娇喘18禁视频| 国产欧美日韩综合在线一区二区| 999精品在线视频| 午夜精品在线福利| 激情视频va一区二区三区| 在线观看午夜福利视频| 高清欧美精品videossex| 露出奶头的视频| 看黄色毛片网站| 国产午夜精品久久久久久| 精品国内亚洲2022精品成人 | 欧美在线一区亚洲| av不卡在线播放| 黄频高清免费视频| 久久久久国产精品人妻aⅴ院 | 咕卡用的链子| 精品国产乱码久久久久久男人| 亚洲一区二区三区不卡视频| 19禁男女啪啪无遮挡网站| 国精品久久久久久国模美| videosex国产| 一区二区三区国产精品乱码| 成年人免费黄色播放视频| 99国产精品99久久久久| 国产欧美亚洲国产| 成人永久免费在线观看视频| а√天堂www在线а√下载 | 久久久国产精品麻豆| 在线国产一区二区在线| 久久久国产精品麻豆| 91精品国产国语对白视频| videosex国产| 一级毛片精品| 久久国产精品大桥未久av| 成人永久免费在线观看视频| 男女之事视频高清在线观看| 亚洲国产精品合色在线| 日韩人妻精品一区2区三区| 动漫黄色视频在线观看| av福利片在线| av中文乱码字幕在线| 欧美丝袜亚洲另类 | 黄色a级毛片大全视频| 欧美黑人精品巨大| 中文字幕最新亚洲高清| 99精品欧美一区二区三区四区| 人人妻人人添人人爽欧美一区卜| 国产欧美亚洲国产| 亚洲成人手机| 男女免费视频国产| av免费在线观看网站|