Synthesis,characterization and comparison of polythiophene–carbon nanocomposite materials as Pt electrocatalyst supports for fuel cell applications

A novel polymer–carbon (PTh–C) nanocomposites containing different percentages of polythiophene (10, 20 and 50% (w/w)) and carbon (Vulcan XC-72) was prepared by a facile solution dispersion method and used to support platinum nanoparticles. The effect of using different percentages of polythiophene in nanocomposites and subsequently prepared electrocatalysts was investigated. The resultant electrocatalysts were extensively characterized by physical (X-ray diffraction (XRD) and transmission electron microscopy (TEM)) and electrochemical (cyclic voltammetry (CV)) techniques. The TEM results showed that the fine Pt nanoparticles prepared by ethylene glycol (EG) method were distributed on the surface of the 50% PTh–C nanocomposites successfully. From the XRD patterns, the average size of dispersed Pt nanoparticles with the face-centered cubic (fcc) structure on 50% PTh–C, 20% PTh–C, 10% PTh–C and carbon were about 4.9, 5.2, 5.4 and 6.1 nm, respectively. The conductivity of PTh–C with different percentages of pure PTh was compared with the conductivity of the corresponding support of pure PTh. It is observed that the conductivity of 50% PTh–C nanocomposites is about 600 times higher than that of pure PTh. Finally, CV measurements of hydrogen and methanol oxidations indicated that Pt/50% PTh–C had a higher electrochemical surface area and higher catalytic activity for methanol oxidation reaction compared to other electrocatalysts. These measurements showed that the Pt/50% PTh–C electrocatalyst by the value of 3.85 had higher \(I_{\mathrm{f}}/I_{\mathrm{b}}\) ratio with respect to Pt/10% PTh–C and Pt/20% PTh–C by the values of 2.66 and 2.0, respectively.     

Activity of PtSnRh/C nanoparticles for the electrooxidation of C1 and C2 alcohols

A systematic investigation of alcohol adsorption and oxidation on binary and ternary electrocatalysts in acid medium was performed. Binary (PtRh) and ternary (PtRhSn) were prepared by the Pechini modified method on carbon Vulcan XC-72, and different nominal compositions were characterized by energy dispersive X-ray and X-ray diffraction (XRD) techniques. The XRD results showed that the Pt₈₀Rh₂₀/C and Pt₇₀Sn₁₀Rh₂₀/C electrocatalysts consisted of the Pt displaced phase, suggesting the formation of a solid solution between the metals Pt/Rh and Pt/Sn.Electrochemical investigations on these different electrode materials were carried out as a function of the electrocatalyst composition, in acid medium (0.5 mol dm^− 3 H₂SO₄), and in the absence and presence of different alcohols (methanol, ethanol and ethylene glycol). The electrochemical results obtained at room temperature have shown that the Pt₇₀Sn₁₀Rh₂₀/C catalyst display better catalytic activity for alcohol oxidation compared with the binary catalyst.In situ reflectance infrared spectroscopy measurements have shown that the oxidation of alcohols mentioned produced CO₂ at low potentials indicating that the materials synthesized could be used as efficient anodes in the fuel cell applications.     

Nanocomposite for methanol oxidation: synthesis and characterization of cubic Pt nanoparticles on graphene sheets

Abstract

We present our recent results on Pt nanoparticles on graphene sheets (Pt-NPs/G), a nanocomposite prepared with microwave assistance in ionic liquid 2-hydroxyethanaminiumformate. Preparation of Pt-NPs/G was achieved without the addition of extra reductant such as hydrazine or ethylene glycol. The Pt nanoparticles on graphene have a cubic-like shape (about 60 wt% Pt loading, Pt-NPs/G) and the particle size is 6 ± 3 nm from transmission electron microscopy results. Electrochemical cyclic voltammetry studies in 0.5 M aqueous H₂SO₄ were performed using Pt-NPs/G and separately, for comparison, using a commercially available electrocatalyst (60 wt% Pt loading, Pt/C). The electrochemical surface ratio of Pt-NPs/G to Pt/C is 0.745. The results of a methanol oxidation reaction (MOR) in 0.5 M aqueous H₂SO₄ + 1.0 M methanol for the two samples are presented. The MOR results show that the ratios of the current density of oxidation (I_f) to the current density of reduction (I_b) are 3.49 (Pt-NPs/G) and 1.37 (Pt/C), respectively, with a preference by 2.55 times favoring Pt-NPs/G. That is, the tolerance CO poisoning of Pt-NPs/G is better than that of commercial Pt/C.     

Pt/C催化剂制备及CO催化氧化性能研究

采用大气压介质阻挡放电辅助氢气热还原方法和氢气热还原方法制备Pt/C催化剂,考察了制备方法及Pt负载量对Pt/C催化性能的影响。采用X-射线衍射(XRD)、循环伏安法、CO催化氧化反应研究Pt/C催化剂的晶相结构、电催化性能和CO催化氧化活性。结果表明:大气压介质阻挡放电辅助氢气热还原所制备的样品具有更高的电化学活性和CO催化氧化活性。当Pt负载量在2%到10%之间变化时,Pt/C-PC催化活性随负载量增加而增加。XRD测试结果显示当Pt负载量为2%,5%和10%时,Pt粒径分别为:10.6 nm,9.1 nm和6.4 nm,说明采用等离子体辅助氢气热还原方法制备的Pt/C-PC催化剂,Pt负载量越大,Pt粒径越小,CO催化氧化活性更高。     

Nonionic surfactant-templated mesoporous carbon as an electrocatalyst support for methanol oxidation

Two carbons were synthesized for use as platinum electrocatalyst supports for methanol oxidation. For both materials, furfuryl alcohol was used as the carbon precursor; however, one (CPEG) was made using poly ethylene glycol as the pore former, while the other (CSRF) was produced using Pluronic^® F127 as the soft template by organic–organic self-assembly. The CPEG and CSRF carbons were estimated from nitrogen physisorption experiments to be micro- and mesoporous, respectively. Platinum nanoparticles were deposited on each carbon as well as on Vulcan XC-72 carbon by the formic acid reduction method. The physicochemical properties of electrocatalysts were studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy dispersive X-ray analysis (EDX), and their electrochemical features were examined using cyclic voltammetry, chronoamperometry, and impedance spectroscopy. It was found that higher methanol oxidation peak current densities as well as lesser charge transfer resistance at electrode/electrolyte interface were obtained for Pt supported on CSRF as compared to those on Vulcan XC-72 carbon, owing to the higher specific surface area and larger total pore volume (696 m² g⁻¹ and 0.60 cm³ g⁻¹, respectively) together with superior electrical conductivity of mesoporous CSRF. On the other hand, the lower surface area and pore volume of microporous CPEG substrate confined Pt nanoparticles deposition and thus made CPEG-supported Pt an inefficient methanol oxidation electrocatalyst.     

Use of single wall carbon nanohorns in polymeric electrolyte fuel cells

Single wall carbon nanohorns (SWNH), produced by AC arc discharge in air, were used as Pt and PtRu supports in polymer electrolyte membrane fuel cells (PEMFC). These electrocatalysts were compared with equivalent electrocatalysts supported on commercial carbon back. The SWNH were characterized by differential thermal analysis (DTA), TEM, SEM, and XRD. The produced SWNH were 84.5 wt% pure, containing 3 wt% of amorphous carbon and 12.5 wt% of graphitic carbon. SWNH were used as electrocatalyst supports and tested in the electrodes of two types of polymer electrolyte fuel cells: H₂-fed PEMFC and direct methanol fuel cells (DMFC). The electrocatalyst nanoparticles anchored on both carbon supports were ca. 2.5 nm in diameter obtained by employing ethylene glycol as the reducing agent. The use of SWNH showed catalytic activities 60% higher than using carbon black as the electrocatalyst support in both types of fuel cells.     

浸渍溶液中有机组分对Pt-Ru/C催化剂性能的影响

采用浸渍还原法制备Pt-Ru/C催化剂,选用不同的有机组分（如乙醇、异丙醇、四氢呋喃和乙二醇）组成浸渍溶液.这些有机组分与前驱体（PtC l62-和Ru^3＋离子）形成的配合物空间位阻的不同,直接影响前驱体在载体表面的吸附状况和还原电位,进而影响粒子尺寸、晶体结构和Pt-Ru/C催化剂的性能.实验表明,采用等体积比的乙二醇和水混合溶剂制备的Pt-Ru/C催化剂,透射电镜测试Pt-Ru粒子的平均粒径为2.7 nm,且粒径分布均匀;X射线衍射分析表明,Pt-Ru粒子相对结晶度低（IPt/IC=1.67）,合金化程度较高（Pt-Ru合金中Ru原子分数为0.471）.在0.5 mol/L H2SO4和0.5 mol/L CH3OH混合溶液中的循环伏安测试表明,所制备的Pt-Ru/C具有良好的催化活性和抗CO中毒能力.     

Carbon supported silver (Ag/C) electrocatalysts for alkaline membrane fuel cells

This study reports on the performance of activated carbon supported silver catalyst (Ag/C) as electrocatalyst in an alkaline membrane fuel cell (AMFC), using alkalized poly (styrene ethylene butylene poly styrene) [APSEBS] as the electrolyte membrane. Carbon supported silver catalyst (Ag/C) with different metal loading was synthesized by means of wet impregnation method. The prepared electrocatalyst was characterized by X-ray diffraction pattern (XRD), thermogravimetric analysis (TGA), UV–Visible diffuse reflectance spectra (DRS-UV) and Raman spectroscopy. Surface morphology analysis of the prepared electrocatalyst using scanning electron microscopy (SEM) revealed the heterogeneous distribution of Ag on carbon support. The performance of the prepared electrocatalyst was evaluated with a home made AMFC using a novel anion exchange membrane (APSEBS). A maximum cell voltage and power density of 0.69 V and 109 mW/cm², respectively, was achieved at 60 °C for the home made 10 wt% (Ag/C) cathode catalyst and anion exchange membrane. Further, the prepared electrocatalyst was subjected to cyclic voltammetry studies to evaluate the methanol oxidation for Direct methanol alkaline fuel cell (DMAFC) applications.     

Mo掺杂对Pt/C催化剂乙醇氧化催化性能的影响

直接乙醇燃料电池(DEFC)由于其高能量密度、绿色无污染等优势受到广泛关注, 寻找和开发具有高乙醇氧化催化活性和抗CO中毒能力的阳极催化剂对DEFC的未来发展和商业应用具有重要意义。本研究采用微波法合成了一系列Mo掺杂的Pt/C催化剂, 并通过循环伏安法、交流阻抗法、计时电流法等电化学技术考察了Mo的掺杂量对Pt/C催化剂乙醇氧化催化活性和稳定性的影响。结果表明: Pt₂Mo/C催化剂在乙醇氧化催化过程中表现出与Pt/C相当的起始电位、最大的峰电流密度和最慢的衰减速度, 说明该催化剂具有最高的乙醇氧化催化活性和最稳定的工作性能。     

Preparation and catalytic activity of Pt/C materials via microwave irradiation

Microwave heating was employed to prepare highly dispersed Pt/C catalyst. Uniform platinum nanoparticles with average diameter of about 3.0-5.0 nm dispersed on carbon materials (XC-72) were synthesized using a domestic microwave oven. Synthesized Pt/C materials were characterized by X-ray diffraction and transmission electron microscopy. The particle size and size distribution of Pt nanoparticles greatly depend on microwave irradiation duration, where the heating temperature rises rapidly as the process proceeds. Cyclic voltammetry demonstrates that Pt/C catalysts derived from microwave irradiation for 90 s exhibits higher catalytic activity than a commercial Pt/C catalyst (E-Tek) at room temperature. The improvement in electrocatalytic activity of synthesized Pt/C materials is attributed to uniformity of particle size, well dispersion and high surface area, which is obtained around 175 °C and irradiation for 90 s.     

Effect of ceria on carbon supported platinum catalysts for methanol electrooxidation

Pt–CeO₂/C catalysts were synthesized by a one-step microwave polyol process and compared with Pt/C (E-TEK) catalyst in terms of the electrochemical activity for methanol oxidation using the cyclic voltammetry and chronoamperometry. The results demonstrated that Pt–CeO₂/C catalysts exhibited lower onset potential, higher current peak and better stability for methanol electrooxidation than Pt/C (E-TEK) catalyst. The effect of ceria on the catalytic activity was investigated by electrochemical measurements and the highest electrochemical activity was obtained at the molar ratio of Pt to Ce by 2:1. The preliminary mechanism of the enhanced electrocatalytic performance for methanol oxidation was discussed.     

反胶束法制备PEMFC用Pt-Ru／C催化剂

采用反胶柬法制备质子交换膜燃料电池（PEMFC）用Pt-Ru／C催化剂．反胶柬体系由环己烷、水、表面活性剂和正辛醇组成．研究了反胶束体系中水与表面活性剂的物质的量之比（ω）、不同类型的表面活性剂和不同还原剂等因素对Pt-Ru／c催化剂性能的影响．研究表明,采用SDS为表面活性剂,控制ω值在适宜的范围内,采用强还原剂KHB4,在室温下反应,可得到粒径小、分布均匀的Pt-Ru／c催化剂．透射电镜（TEM）测试结果表明,Pt—Ru粒子的平均粒径为3．1nm;X射线衍射（XRD）分析表明,Pt—Ru／c催化剂合金化程度高,相对结晶度为3．1;能量散射能谱（EDS）分析表明,形成的Pt和Ru的含量接近实验设定值在0．5mol／L的H2SO4以及与0．5mol／L的CH3OH混合溶液中的循环伏安测试结果表明,自制Pt—Ru／C催化剂与Johnson公司商品Pt—Ru／C催化剂的电化学性能相近。     

Influence of water-organic solvent composition on composition and structure of Pt/C and Pt<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni/C electrocatalysts in borohydride synthesis

Nanostructured Pt/C and Pt _x Ni/C materials containing from 4 to 30 wt % Pt were prepared using the method of chemical reduction of platinum and nickel compounds in the liquid phase by sodium borohydride solution. The change in the nature of the organic component (ethylene glycol, dimethyl sulfoxide, dimethyl formamide, tetrahydrofuran, acetone, ethyl alcohol, and glycerin) of binary water-organic solvent influences considerably the reaction product yield, structural characteristics (average nanoparticle size) of the material, mass fraction of metals in the nanocomposite, and the PtNi alloy composition. The fundamental possibility of controlling the PtNi alloy composition and structural characteristics of Pt/C and Pt _x -Ni/C nanocomposites by variation of the water-organic solvent composition was demonstrated. The minimum average size of nanoparticles in synthesized metal-carbon materials promising as electrocatalysts in low-temperature fuel cells was 2 nm for Pt/C (for about 20 wt % Pt) and 1.8 nm for Pt₂Ni (for about 30 wt % Pt).     

铂/石墨烯复合材料的合成及性能表征

以天然鳞状石墨为原料,采用化学氧化法合成氧化石墨,再经低温热解膨胀得到膨胀石墨;采用微波加热乙二醇法同时还原膨胀石墨和PtClO2-6离子得到铂/石墨烯(Pt/Gr)复合材料.分析了反应前溶液的pH值、微波加热时间以及乙二醇中水含量对Pt/Gr结构及催化性能的影响.通过循环伏安法对Pt/Gr的电化学性能进行了表征.采用透射电镜和扫描电镜观察了Gr和Pt/Gr的表面结构.研究结果表明,在优化的实验条件下可以得到高负载量高分散性的Pt/Gr纳米复合材料.实验得到的40％(质量分数)Pt/Gr的Pt粒子粒径分布在3.0～3.3nm范围内,对氢电极和氧电极反应有高催化活性,可作为质子交换膜燃料电池的电催化剂.     

Electrocatalytic activity of PtAu/C catalysts for glycerol oxidation

The electrocatalytic oxidation of glycerol on PtAu/C catalysts has been investigated by cyclic voltammetry. PtAu bimetallic nanoparticles are prepared by chemical reduction. Carbon-supported PtAu catalysts are found to exhibit high electrocatalytic activity for the oxidation of glycerol in alkaline solution in terms of oxidation potential and current density as well as stability, and PtAu/C catalysts with different Pt:Au composition ratios show no much difference in catalytic activity. In acidic solution, PtAu/C catalysts exhibit similar to Pt/C catalysts in activity, but the advantage of the PtAu/C catalysts in terms of per unit mass of platinum is still obvious. The PtAu/C catalysts, in a wide Pt:Au ratio range, show a remarkable enhancement in the mass specific activity of platinum with decreasing platinum content in both alkaline and acidic solutions. This is of significance for reducing the usage of platinum and indicates that though platinum acts as main active sites, gold also plays an important role in the function of PtAu/C catalysts.     

Solvothermal-assisted morphology evolution of nanostructured LiMnPO4 as high-performance lithium-ion batteries cathode

As a potential substitute for LiFePO_4, LiMnPO_4 has attracted more and more attention due to its higher energy, showing potential application in electric vehicle(EV) or hybrid electric vehicle(HEV). In this work,solvothermal method was used to prepare nano-sized LiMnPO_4, where ethylene glycol was used as solvent, and lithium acetate(LiAc), phosphoric acid(H_3 PO_4) and manganese chloride(MnCl_2) were used as precursors. The crystal structure and morphology of the obtained products were characterized by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The electrochemical performance was evaluated by charge-discharge cycling, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the molar ratio of LiAc:H_3 PO_4:MnCl_2 plays a critical role in directing the morphology of LiMnPO_4. Large plates transform into irregular nanoparticles when the molar ratio changes from 2:1:1 to 6:1:1. After carbon coating, the product prepared from the 6:1:1 precursor could deliver discharge capacities of 156.9,122.8, and 89.7 mAhg-1 at 0.05 C, 1 C and 10 C, respectively.The capacity retention can be maintained at 85.1% after 200 cycles at 1 C rate for this product.     

Convenient immobilization of Pt-Sn bimetallic catalysts on nitrogen-doped carbon nanotubes for direct alcohol electrocatalytic oxidation

Pt-Sn alloy nanoparticles were conveniently immobilized on nitrogen-doped carbon nanotubes (NCNTs) through microwave-assisted ethylene glycol reduction. The nanoparticles have a narrow particle size distribution with the average particle size around 3 nm as measured by transmission electron microscopy and x-ray diffraction. The binding energy of metallic Sn passively shifts due to the charge transfer from Sn to Pt, as revealed by x-ray photoelectron spectroscopy. In comparison with the commercial Pt/C catalyst, Pt/NCNT presents a clear increase in activity for alcohol electro-oxidation due to the improved support, while the bimetallic Pt-Sn/NCNT has even higher activity owing to the alloying of Pt with Sn. Both Pt-Sn/NCNT and Pt/NCNT catalysts exhibit competitive long-term stability to Pt/C catalyst. The low cost, simple preparation and superior electrocatalytic performance indicate the great potential of Pt-Sn/NCNT in direct alcohol fuel cells.     

Highly dense and uniformly dispersed platinum nanoparticles on poly(acrylic acid) modified multi-walled carbon nanotubes for methanol oxidation

Poly(acrylic acid) modified multi-walled carbon nanotubes (PAA-MWNTs) were synthesized through in situ radical polymerization in acetone and the PAA-MWNTs were used as supporting material for platinum nanoparticles. Platinum nanoparticles were deposited on the surface of PAA-MWNTs with high loading and high dispersion through ethylene glycol reduction. The size of Pt nanoparticles on PAA-MWNTs can be tuned by the water content in the reaction system and the loading amount can be adjusted by the mass ratio of H₂PtCl₆ to PAA-MWNTs. The electrocatalytic properties of the Pt/PAA-MWNTs catalyst were evaluated by methanol oxidation. The results of cyclic voltammetry show that the Pt/PAA-MWNTs composite possesses high electrocatalytic activity, good long-term stability and storage property, which can be attributed to the small particle size and high dispersion of Pt nanoparticles as well as the nature of MWNTs.     

Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells

PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.     

PEMFC用抗溺水性功能化Pt/C催化剂的制备及表征

催化剂的碳载体腐蚀是Pt/C催化剂催化性能下降的重要原因,并且亲水性的催化剂增加了质子交换膜燃料电池氧电极发生水淹的风险。利用过氧化氢对XC-72碳进行氧化预处理,负载Pt后,进一步用水合肼对Pt/C催化剂还原,制备耐蚀性和抗溺水性的Pt/C催化剂。对红外光谱吸收峰进行比较可知,经双氧水处理后,XC-72碳表面的含氧官能团数量增加,其接触角小于未经处理的XC-72碳;进一步用水合肼还原氧化后的XC-72碳,接触角较氧化的XC-72碳增大22.4°,抗溺水性增强。由比表面积测定可知,双氧水处理XC-72碳,比表面积下降,但中孔比例增加,有利于Pt的负载。水合肼还原后的Pt/C催化剂较还原之前的Pt/C催化剂抗溺水性增强,接触角增大6.2°。经2000周次循环伏安扫描,水合肼还原后的Pt/C催化剂电化学比表面损失减小,耐久性提高。