Nanostructured PtRu/C as anode catalysts prepared in a pseudomicroemulsion with ionic surfactant for direct methanol fuel cell

Nanostructured PtRu/C catalysts have been prepared from a water-in-oil pseudomicroemulsion with the aqueous phase of a mixed concentrated solution of H(2)PtCl(6), RuCl(3), and carbon powder, oil phase of cyclohexane, ionic surfactant of sodium dodecylbenzene sulfonate (C(18)H(29)NaO(3)S), and cosurfactant n-butanol (C(4)H(10)O). Two different composing PtRu/C nanocatalysts (catalyst 1, Pt 20 wt %, Ru 15 wt %; catalyst 2, Pt 20 wt %, Ru 10 wt %) were synthesized. The catalysts were characterized by transmission electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis, and the particles were found to be nanosized (2-4 nm) and inherit the Pt face-centered cubic structure with Pt and Ru mainly in the zero valance oxidation state. The ruthenium oxide and hydrous ruthenium oxide (RuO(x)()H(y)()) were also found in these catalysts. The cyclic voltammograms (CVs) and chronoamperometries for methanol oxidation on these catalysts showed that catalyst 1 with a higher Ru content (15 wt %) has a higher and more durable electrocatalytic activity to methanol oxidation than catalyst 2 with low Ru content (10 wt %). The CV results for catalysts 1 and 2 strongly support the bifunctional mechanism of PtRu/C catalysts for methanol oxidation. The data from direct methanol single cells using these two PtRu/C as anode catalysts show the cell with catalyst 1 has higher open circuit voltage (OCV = 0.75 V) and maximal power density (78 mW/cm(2)) than that with catalyst 2 (OCV = 0.70 V, P(max) = 56 mW/cm(2)) at 80 degrees C.     

Anodic activation of PtRu/C catalysts for methanol oxidation

Anodic treatment of PtRu/C catalysts in 0.5 M sulfuric acid at 1.3 V (vs RHE) for 0.5 h was found able to promote the activity for methanol oxidation by a few tenths to 5 times. This anodic activation effect was valid for samples domestically prepared under different conditions and that produced by Johnson-Matthey. On the basis of the changes of cyclic voltammetry during the anodic treatment, a model was proposed for the activation effect. According to the model, there are two categories of ruthenium oxides in the catalyst: one is electrochemically reversible and beneficial for catalytic activity, while the other is irreversible and harmful. During the anodic treatment, the harmful oxide is decreased, while the beneficial oxide either increased or changed only slightly, resulting in a beneficial net change.     

Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.     

铂、钌共修饰碳纳米管电极的制备及对甲醇的电催化氧化

碳纳米管以其独特的结构,良好的电性能和机械性能吸引了众多的关注~([1]),被认为是潜在的异相催化剂载体 ~([2]).近来关于碳纳米管负载催化剂的合成及其在异相催化中应用的研究已见报道~([3]).     

Multiwalled carbon nanotube supported PtRu for the anode of direct methanol fuel cells

The activity of the methanol oxidation reaction of a multiwalled carbon nanotube (MWCNT)-supported PtRu catalyst was investigated and compared with the Vulcan XC-72 carbon-supported catalyst. The PtRu nanoparticles with 1:1 and 7:3 atomic ratios (with similar PtRu loadings and morphological structures) were deposited both on the MWCNTs and on the carbon. Cyclicvoltammetry results demonstrated that the MWCNT-supported PtRu catalyst exhibited a higher mass activity (mA mg(-1) of PtRu) for the methanol oxidation reaction than the carbon-supported PtRu under the condition that both catalysts possess more or less the same PtRu loadings, particle sizes, dispersions, and electrochemical surface area. The direct methanol fuel cell performance test data showed that MWCNT-supported PtRu catalysts yielded about 35-39% higher power densities than the carbon-supported PtRu.     

Promotion of PtRu/C anode catalysts for ethanol oxidation reaction by addition of Sn modifier

PtRu/C anode electrocatalysts modified by Sn were prepared for ethanol oxidation reaction (EOR). Their phase structures, surface species, surface compositions, and EOR activities were characterized by XRD, XPS, temperature-programmed reduction (TPR), and CV, respectively. It has been found that in the PtRu/Sn_xC and PtSn/C alloy catalysts, some Sn alloyed with Pt to form Pt–Sn phase existed as the metallic state, however, the excess Sn existed as the amorphous SnO or crystalline SnO₂. Surface analyses and electrochemical measurements suggest that the surface Ru and amorphous SnO instead of the crystalline SnO₂ are important species for the promotion of EOR. As a result, compared with PtSn/C, the I₀₆ was enhanced about 200% for the PtRu/C electrocatalyst with 10 wt% of Sn modification.     

Structural analysis of sonochemically prepared PtRu versus Johnson Matthey PtRu in operating direct methanol fuel cells

Sonochemically prepared PtRu (3 : 1) and Johnson Matthey PtRu (1 : 1) were analyzed by X-ray absorption spectroscopy in operating liquid feed direct methanol fuel cells. The total metal loadings were 4 mg cm(-2) unsupported catalysts at the anode and cathode of the membrane electrode assembly. Ex situ XRD lattice parameter analysis indicates partial segregation of the Ru from the PtRu fcc alloy in both catalysts. A comparison of the in situ DMFC EXAFS to that of the as-received catalyst shows that catalyst restructuring during DMFC operation increases the total metal coordination numbers. A combined analysis of XRD determined grain sizes and lattice parameters, ex situ and in situ EXAFS analysis, and XRF of the as-received catalysts enables determination of the catalyst shell composition. The multi-spectrum analysis shows that the core size increases during DMFC operation by reduction of Pt oxides and incorporation of Pt into the core. This increases the mole fraction of Ru in the catalyst shell structure.     

Pt-Ru supported on double-walled carbon nanotubes as high-performance anode catalysts for direct methanol fuel cells

Pt-Ru supported on carbon nanotubes (CNTs) (single-walled nanotubes, double-walled nanotubes (DWNTs), and multi-walled nanotubes) catalysts are prepared by an ethylene glycol reduction method. Pt-Ru nanoparticles with a diameter of 2-3 nm and narrow particle size distributions are uniformly deposited onto the CNTs. A simple and fast filtration method followed by a hot-press film transfer is employed to prepare the anode catalyst layer on a Nafion membrane. The Pt-Ru/DWNTs catalyst shows the highest specific activity for methanol oxidation reaction in rotating disk electrode experiments and the highest performance as an anode catalyst in direct methanol fuel cell (DMFC) single cell tests. The DMFC single cell with Pt-Ru/DWNTs (50 wt %, 0.34 mg Pt-Ru/cm(2)) produces a 68% enhancement of power density, and at the same time, an 83% reduction of Pt-Ru electrode loading when compared to Pt-Ru/C (40 wt %, 2.0 mg Pt-Ru/cm(2)).     

Poly(vinylpyrrolidone)-modified graphite carbon nanofibers as promising supports for PtRu catalysts in direct methanol fuel cells

Carbon nanomaterials, including herringbone graphite carbon nanofibers (GNFH), multiwalled carbon nanotubes (MWCNT), and carbon black, were surface-modified by a new poly(vinylpyrrolidone) (PVP) grafting process as well as by the conventional acid-oxidation (AO) process, and characterized by FTIR, TGA, Raman, HRTEM, XRD, and XPS measurements. Pt nanoparticles of 1.8 nm were evenly deposited on all PVP-grafted carbon nanomaterials. The effects of the two surface modification processes on the dispersion, average Pt nanoparticle sizes, the electrocatalytic performance, and electrical conductivities of Pt-carbon nanocomposites in direct methanol oxidation were systematically studied and compared. It was found that the PVP-grafted carbon nanomaterials have much less loss in the electric conductivity and thus better electrocatalytic performance, 17-463% higher, than their corresponding acid oxidation-treated nanocomposites. The electrocatalytic performance of the Pt-carbon nanocomposites decreases in the following order: Pt-PVP-GNFH > Pt-PVP-MWCNTarc > Pt-AO-MWCNTarc > Pt-PVP-MWCNTCVD > Pt-AO-MWCNTCVD > Pt-XC-72R > Pt-AO-GNFH, with the Pt-PVP-GNFH nanocomposite having approximately 270% higher performance than that of the Pt-Vulcan XC-72R nanocomposite. In addition, PtRu-PVP-GNFH shows even better (50% higher) electrocatalytic activity than the Pt-PVP-GNFH nanocomposite at a 0.6 V applied voltage.     

Small-sized and contacting Pt-WC nanostructures on graphene as highly efficient anode catalysts for direct methanol fuel cells

The synergistic effect between Pt and WC is beneficial for methanol electro-oxidation, and makes Pt-WC catalyst a promising anode candidate for the direct methanol fuel cell. This paper reports on the design and synthesis of small-sized and contacting Pt-WC nanostructures on graphene that bring the synergistic effect into full play. Firstly, DFT calculations show the existence of a strong covalent interaction between WC and graphene, which suggests great potential for anchoring WC on graphene with formation of small-sized, well-dispersed WC particles. The calculations also reveal that, when Pt attaches to the pre-existing WC/graphene hybrid, Pt particles preferentially grow on WC rather than graphene. Our experiments confirmed that highly disperse WC nanoparticles (ca. 5?nm) can indeed be anchored on graphene. Also, Pt particles 2-3?nm in size are well dispersed on WC/graphene hybrid and preferentially grow on WC grains, forming contacting Pt-WC nanostructures. These results are consistent with the theoretical findings. X-ray absorption fine structure spectroscopy further confirms the intimate contact between Pt and WC, and demonstrates that the presence of WC can facilitate the crystallinity of Pt particles. This new Pt-WC/graphene catalyst exhibits a high catalytic efficiency toward methanol oxidation, with a mass activity 1.98 and 4.52 times those of commercial PtRu/C and Pt/C catalysts, respectively.     

PtRu/Ti anodes with varying Pt ratio: Ru ratio prepared by electrodeposition for the direct methanol fuel cell

PtRu/Ti anodes with varying Pt ratio Ru ratio were prepared by electrodeposition of a thin PtRu catalyst layer onto Ti mesh for a direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX and XRD. The catalyst coating layer shows an alloy character. The relative activities of the PtRu/Ti electrodes were assessed and compared in half cell and single DMFC experiments. The results show that these electrodes are very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 9 at.% for DMFC operating at 20 degrees C and 11 at.% at 60 degrees C. The PtRu/Ti anode shows a performance comparable to that of the conventional carbon-based anode in a DMFC operating with 0.25 M or 0.5 M methanol solution and atmosphere oxygen gas at 90 degrees C.     

PtRu catalysts supported on heteropolyacid and chitosan functionalized carbon nanotubes for methanol oxidation reaction of fuel cells

A simple self-assembly approach has been developed to functionalize carbon nanotubes (CNTs) with chitosan (CS) and heteropolyacids (HPAs) of phosphomolybdic acid (H(3)PMo(12)O(40), HPMo) and phosphotungstic acid (H(3)PW(12)O(40), HPW). The non-covalent functionalization method, which introduces homogenous surface functional groups with no detrimental effect on graphene structures of CNTs, can be carried out at room temperature without the use of corrosive acids. The PtRu nanoparticles supported on HPAs-CS-CNTs have a uniform distribution and much smaller size as compared to those of the PtRu nanoparticles supported on conventional acid treated CNTs (PtRu/AO-CNTs). The onset and peak potentials for CO(ad) oxidation on PtRu/HPAs-CS-CNTs catalysts are more negative than those on PtRu/AO-CNTs, indicating that HPAs facilitate the electro-oxidation of CO. The PtRu/HPMo-CS-CNTs catalyst has a higher electrocatalytic activity for methanol oxidation and higher tolerance toward CO poisoning than PtRu/HPW-CS-CNTs. The better electrocatalytic enhancement of HPMo on the PtRu/HPAs-CS-CNTs catalyst is most likely related to the fact that molybdenum-containing HPAs such as HPMo have more labile terminal oxygen to provide additional active oxygen sites while accelerating the CO and methanol oxidation in a similar way to that of Ru in the PtRu binary alloy system.     

PtRu/氮掺杂碳电催化甲醇氧化及电解水析氢性能

将三聚氰胺、RuCl₃及炭黑以一定的比例分散于乙醇中,采用旋转蒸干及高温热处理合成了一种氮掺杂碳(NC)负载Ru的Ru/NC 催化剂。采用硼氢化钠液相化学还原法合成了不同 Pt、Ru 负载量的 PtRu/NC 催化剂,并用于电催化甲醇氧化反应(MOR)及电催化分解水析氢反应(HER)。结果表明,合成的催化剂中 Pt₁Ru/NC(Pt、Ru的实际负载量分别为 1.14%、0.54%)表现出最优的MOR性能,质量活性达4.96 A·mg^-1_PtRu,且经10 000 s稳定性测试后质量活性保持在测试前的91.1%。同时,当电流密度为100 mA·cm^-2时,Pt₁Ru/NC在HER中表现出最低的过电位(103 mV)和最小的Tafel斜率(15.29 mV·dec^-1)。通过X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、电感耦合等离子体发射光谱(ICP‐OES)、STEM‐能谱(STEM‐EDS)技术PtRu/NC双金属催化剂,其具有优异催化性能的原因如下：(1) PtRu双金属纳米颗粒高度分散于NC上;(2) Pt以纳米团簇或单原子形式负载于Ru上,后负载于NC,形成了Pt‐Ru相分离结构;(3) Pt、Ru与N之间存在协同效应。     

PtRu/氮掺杂碳电催化甲醇氧化及电解水析氢性能

将三聚氰胺、RuCl₃及炭黑以一定的比例分散于乙醇中,采用旋转蒸干及高温热处理合成了一种氮掺杂碳(NC)负载Ru的Ru/NC催化剂。采用硼氢化钠液相化学还原法合成了不同Pt、Ru负载量的PtRu/NC催化剂,并用于电催化甲醇氧化反应(MOR)及电催化分解水析氢反应(HER)。结果表明,合成的催化剂中Pt₁Ru/NC(Pt、Ru的实际负载量分别为1.14%、0.54%)表现出最优的MOR性能,质量活性达4.96 A·mg^-1_PtRu,且经10 000 s稳定性测试后质量活性保持在测试前的91.1%。同时,当电流密度为100mA·cm^-2时,Pt₁Ru/NC在 HER中表现出最低的过电位(103 mV)和最小的 Tafel斜率(15.29 mV·dec^-1)。通过 X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、电感耦合等离子体发射光谱(ICP-OES)、STEM-能谱(STEM-EDS)技术表征了PtRu/NC双金属催化剂,其具有优异催化性能的原因如下：(1) PtRu双金属纳米颗粒高度分散于NC上;(2) Pt以纳米团簇或单原子形式负载于Ru上,后负载于NC,形成了Pt-Ru相分离结构;(3) Pt、Ru与N之间存在协同效应。     

PtRu/carbon nanotube nanocomposite synthesized in supercritical fluid: a novel electrocatalyst for direct methanol fuel cells

Platinum/ruthenium nanoparticles were decorated on carbon nanotubes (CNT) in supercritical carbon dioxide, and the nanocomposites were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). TEM images show that the particles size is in the range of 5-10 nm, and XRD patterns show a face-centered cubic crystal structure. Methanol electrooxidation in 1 M sulfuric acid electrolyte containing 2 M methanol were studied onPtRu/CNT (Pt, 4.1 wt%; Ru, 2.3 wt%; molar ratio approximately Pt/Ru = 45:55) catalysts using cyclic voltammetry, linear sweep voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. All the electrochemical results show that PtRu/CNT catalysts exhibit high activity for methanol oxidation which resulted from the high surface area of carbon nanotubes and the nanostructure of platinum/ruthenium particles. Compared with Pt/CNT, the onset potential is much lower and the ratio of forward anodic peak current to reverse anodic peak current is much higher for methanol oxidation, which indicates the higher catalytic activity of PtRu/CNT. The presence of Ru with Pt accelerates the rate of methanol oxidation. The results demonstrated the feasibility of processing bimetallic catalysts in supercritical carbon dioxide for fuel cell applications.     

Highly stable PtRuTiOx/C anode electrocatalyst for direct methanol fuel cells

In the present investigation, PtRuTiO_x/C electrocatalyst was prepared by a modified polyol synthesis method and the as-prepared electrocatalyst was treated under the reductive atmosphere (30 vol% H₂ in Ar) at 500 °C for 2 h (denoted as PtRuTiO_x/C-500) to enhance the interaction between the metal particles and the support. For comparison, the commercial PtRu/C electrocatalyst was also treated by the same procedure as PtRuTiO_x/C (denoted as PtRu/C-500). Transmission electron microscopy results indicated that PtRuTiO_x/C electrocatalyst exhibited not only a uniform dispersion and narrow size distribution with a smaller particle size, but also excellent stability during the thermal treatment. In contrast, the commercial PtRu/C electrocatalyst is not stable during the thermal treatment and the metal particles greatly agglomerated. The results of CO-stripping voltammetry, single direct methanol fuel cell tests and life-time test jointly showed that PtRuTiO_x/C-500 had better durability than commercial PtRu/C while keeping a desirable activity toward methanol electro-oxidation, which may be attributed to the addition of titanium oxide that improved the interaction between noble metal particles and the support.     

Catalytic activity and stability toward methanol oxidation of PtRu/CNTs prepared by adsorption in aqueous solution and reduction in ethylene glycol

In this paper, we reported an improved process for the preparation of PtRu/CNTs, which involves the adsorption of Pt and Ru ions on CNTs in aqueous solution and the reduction of the adsorbed Pt and Ru ions on CNTs in ethylene glycol. The surface morphology, structure, and compositions of the prepared catalyst were studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), and energy-dispersive spectrometer. TEM observation showed that the particles size of the prepared PtRu alloy was in the range of 2–5 nm, XRD patterns confirmed a face-centered cubic crystal structure. The activity and stability of the prepared catalyst toward methanol oxidation were studied in 0.5 M H₂SO₄ + 1 M CH₃OH solution by cyclic voltammetry, chronoamperometry, and chronopotentiometry. The electrochemical results showed that the prepared catalyst exhibited higher activity and stability toward methanol oxidation than commercial PtRu/C with the same loading amount of Pt and Ru.     

Multilayered Pt/Ru nanorods with controllable bimetallic sites as methanol oxidation catalysts

A physical synthesis of multilayered Pt/Ru nanorods with controllable bimetallic sites as methanol oxidation catalysts is reported for the first time. The novel nanorods were synthesized via the oblique angle deposition method, deposited prior to the formation of each individual noble metal layer, in a sequential fashion. It has been shown that the oblique angle deposition controls the morphology and electrochemical properties of the resultant nanostructures. Sequentially the multilayered nanorods comprising Pt and Ru segments exhibited superior electrocatalytic activity when compared to equivalent monometallic Pt nanorods with respect to methanol electrooxidation reaction in an acidic medium. Moreover, it has been established that the electrochemical process takes place at the Pt/Ru nanorods followed the bifunctional mechanism. The relative rates of reaction, recorded using chronoamperometry, show a linear relationship between the long-time current density and the number of Pt/Ru interfaces. Interestingly, the best catalyst for methanol oxidation was found to the surface of bimetallic Pt/Ru nanorods produced by the heat treatments via the so-called electronic effect. This reflects the fact that the ensemble effects of combined bifunctional and electronic effects via second elements could be expected in methanol oxidation reactions. Electrocatalytic activities correlate well with bimetallic pair sites and electronic properties analyzed by X-ray photoemission spectroscopy and X-ray absorption near-edge structure.     

Composite anode catalyst layer for direct methanol fuel cell

A novel composite anode catalyst layer for direct methanol fuel cell is reported in this paper. The dual-layer anode, which is based on the catalyst coated membrane technique, characterizes a morphological variety of the catalyst layer. The inner sub-layer with a dense morphology can effectively suppress methanol crossover. On the other hand, the outer sub-layer modified by the pore-forming agent, NH₄HCO₃ and the carbon nanotubes can enhance the electrochemical surface area and increase the catalyst utilization. The structural improvement of anode catalyst layer results in a 40% increment in maximum power density during the single cell test at 30 °C.