Electro-Deposition Pt Catalysts Supported on Carbon-Nanotubes for Methanol Oxidation

In order to study the properties of supporting Pt catalysts for methanol oxidation,carbon-nanotubes are used by electrochemical deposition method. Different deposition turns,different cyclic voltammetry scanning speeds and processing time with ascorbic acid are investigated in this paper. The micrographs of Pt / CNTs catalysts are characterized by scanning electron microscopy,the electro-catalytic properties of Pt / CNTs catalysts for methanol oxidation are investigated by cycle voltammetry and chronoamperometry. The results show that the size of platinum will be greater with the faster scanning speed. After dissolution in ascorbic acid,Pt nanoparticles disperse uniformly. The obtained Pt / CNTs catalysts show a high electro-catalytic activity and stability.

高电位下PEMFC阴极催化层Pt对碳腐蚀的影响

结合非色散红外光谱(NDIR)和电化学表征的方法研究了质子交换膜燃料电池阴极催化层在0.8 V恒电位下,碳腐蚀的变化规律及其对Pt氧化过程的依赖性。研究发现0.8 V恒电位下,Pt会导致碳载体的腐蚀更加剧烈。运行100 h后,Pt/C电极的碳损失质量达到8.7%,是纯碳电极的3.5倍。Pt/C电极的碳腐蚀规律可以分为三个阶段,第一阶段呈对数增长,第三阶段呈线性增长,中间存在混合增长区。而Pt氧化物累积量分析表明Pt的氧化呈现出两段对数关系,且中间存在一个过渡区,这解释了碳腐蚀的三段规律。活跃的Pt-OH催化碳腐蚀,并快速转化成PtO_(x)等惰性氧化物,大幅降低对碳腐蚀的促进作用,当Pt-OH含量稳定后,碳腐蚀速率达到稳态。电位阶跃工况下,Pt氧化物增长速度明显降低,碳载体质量损失达到了15.55%,几乎是恒电位工况的2倍,表明控制Pt氧化物累积速度会加速碳载体的腐蚀。

Pt基催化剂上CO_(2)辅助丙烷脱氢的反应机理

Pt基双金属是一种具有发展前景的丙烷脱氢催化剂,CO_(2)在Pt基催化剂上辅助丙烷脱氢的微观反应机理与优势能量路径尚不明确,为此,采用密度泛函理论(DFT)计算研究了Pt(111)表面及Pt3Mn(111)表面上丙烷直接脱氢反应(PDH)及CO_(2)辅助丙烷脱氢反应(CO_(2)-ODH)的反应网络与关键步骤。计算结果表明:CO_(2)的加入可以降低PDH速控步骤的能垒,对于消耗表面H有利,促进了丙烷脱氢反应正向移动,有利于生成丙烯,从而改变了反应路径和反应动力学;CO_(2)在消除积炭反应中的能垒较高,但是Mn的引入有利于CO_(2)消除积炭。此外,第二金属组分Mn的引入,不但有利于产物丙烯脱附,还提高了C—C裂解能垒,从而提高了丙烯的选择性。

High-performance proton exchange membrane fuel cell with ultra-low loading Pt on vertically aligned carbon nanotubes as integrated catalyst layer

Reducing a Pt loading with improved power output and durability is essential to promote the large-scale application of proton exchange membrane fuel cells(PEMFCs).To achieve this goal,constructing optimized structure of catalyst layers with efficient mass transportation channels plays a vital role.Herein,PEMFCs with order-structured cathodic electrodes were fabricated by depositing Pt nanoparticles by Ebeam onto vertically aligned carbon nanotubes(VACNTs)growth on Al foil via plasma-enhanced chemical vapor deposition.Results demonstrate that the proportion of hydrophilic Pt-deposited region along VACNTs and residual hydrophobic region of VANCTs without Pt strongly influences the cell performance,in particular at high current densities.When Pt nanoparticles deposit on the top depth of around 600 nm on VACNTs with a length of 4.6μm,the cell shows the highest performance,compared with others with various lengths of VACNTs.It delivers a maximum power output of 1.61 W cm^(-2)(H_(2)/O_(2),150 k Pa)and 0.79 W cm^(-2)(H_(2)/Air,150 k Pa)at Pt loading of 50μg cm^(-2),exceeding most of previously reported PEMFCs with Pt loading of<100μg cm^(-2).Even though the Pt loading is down to 30μg cm^(-2)(1.36 W cm^(-2)),the performance is also better than 100μg cm^(-2)(1.24 W cm^(-2))of commercial Pt/C,and presents better stability.This excellent performance is critical attributed to the ordered hydrophobic region providing sufficient mass passages to facilitate the fast water drainage at high current densities.This work gives a new understanding for oxygen reduction reaction occurred in VACNTs-based ordered electrodes,demonstrating the most possibility to achieve a substantial reduction in Pt loading<100μg cm^(-2) without sacrificing in performance.

New strategy of S,N co‐doping of conductive‐copolymer‐derived carbon nanotubes to effectively improve the dispersion of PtCu nanocrystals for boosting the electrocatalytic oxidation of methanol

Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.

Carbon nanotubes-Nafion composites as Pt-Ru catalyst support for methanol electro-oxidation in acid media

Carbon nanotubes-Nafion （CNTs-Nation） composites were prepared by impregnated CNTs with Nation in ethanol solution and characterized by FT-IR. Pt-Ru catalysts supported on CNTs-Nafion composites were synthesized by microwave-assisted polyol process. The physical and electrochemical properties of the catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, CO stripping voltammetry, cyclic voltammetry （CV） and chronoamperometry （CA）. The results showed that the Nation incorporation in CNTs-Nation composites did not significantly alter the oxygen-containing groups on the CNTs surface. The Pt-Ru catalyst supported on CNTs-Nafion composites with 2 wt% Naton showed good dispersion and the best CO oxidation and methanol electro-oxidation activities.

Phosphorous-Modified Carbon Nanotube-Supported Pt Nanoparticles for Propane Dehydrogenation Reaction

The sintering of Pt nanoparticles is one of the main reasons for catalyst deactivation during the high-temperature propane dehydrogenation(PDH) reaction. Promoters and supports have been introduced to prolong the catalyst life.However, it is still necessary to develop novel catalysts with robust stability. Herein, the phosphorus-modified carbon nanotube-supported Pt nanoparticles were employed for the PDH process. Phosphorus modification improves the Pt dispersion, effectively promoting the activity of Pt/P-CNTs. Additionally, the phosphorus-modified CNTs can interact strongly with Pt nanoparticles by improving the electron transfer or hybridization, stabilizing Pt nanoparticles from agglomeration, and significantly enhancing the catalyst stability.

Pt基催化剂用于丙烷脱氢反应的研究进展

丙烯是一种重要的化工原料,被广泛用于生产聚丙烯、丙烯腈、环氧丙烷等化工产品,也是塑料、橡胶、纤维三大合成材料的基本原料。由于对丙烯的需求量不断增长以及页岩气的广泛开采,丙烷脱氢(PDH)作为一种直接生产丙烯的工业技术备受关注。然而,商业上使用的铂(Pt)基催化剂活性组分容易烧结和团聚,导致积碳问题,很容易失去催化活性。因此,开发具有高活性和高稳定性的PDH催化剂具有重要意义。近年来,负载型Pt基催化剂在PDH反应中得到了广泛研究。从金属助剂优化和载体效应两个角度,综述了当前Pt基PDH催化剂的研究进展,特别是助剂和载体如何使Pt中心形成高度分散和稳定的活性位点,并系统总结了提高Pt基催化剂稳定性的策略。此外,还展望了Pt基催化剂在PDH反应中的发展方向。

Facile Fabrication of Platinum Nanoparticles Supported on Nitrogen-doped Carbon Nanotubes and Their Catalytic Activity

A facile impregnation method under mild condition is designed for synthesis of highly dispersed Pt nanoparticles with a narrow size of 4-7 nm on nitrogen-doped carbon nanotubes （CNx）. CNx do not need any pre-surface modification due to the inherent chemical activity. The structure and nature of Pt/CNx were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy spectrum. All the experimental results revealed that the large amount of doped nitrogen atoms in CNx was virtually effective for capturing the Pt（IV） ions. The improved surface nitrogen functionalities and hydrophilicity contributed to the good dispersion and immobi- lization of Pt nanoparticles on the CNx surface. The Pt/CNx served as active and reusable catalysts in the hydrogenation of allyl alcohol. This could be attributed to high dispersion of Pt nanoparticles and stronger interaction between Pt and the supports, which prevented the Pt nanoparticles from aggregating into less active Pt black and from leaching as well.

A Novel Carbon Nanotube-Supported NiP Amorphous Alloy Catalyst and Its Hydrogenation Activity

A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.

Preparation and Characterization of Carbon Nanotubes-Coated Cordierite for Catalyst Supports

The carbon nanotubes-coated cordierite （CNTs-cordierite） was fabricated by pyrolysis of ethine on cordierite with iron catalyst, which was penetrated into the cordierite substrate by vacuum impregnation. The cordierite substrate, carbon naontubes, and CNTs-cordierite were characterized by SEM, TEM/HREM, BET, and TGA. The results show that the carbon nanotubes were distributed uniformly on the surface of cordierite. A significant increase in BET surface area and pore volume was observed, and a suitable pore-size distribution was obtained. On the CNTs-cordierite, carbon nanotubes penetrated into the cordierite substrate, which led to a remarkable stability of the CNTs against ultrasound maltreatment. Growth time is an important factor for thermostability and texture of the sample. The mass increased but the purity decreased with the growth time, which caused the exothermic peak shift to low temperature, and the corresponding full width half maximum （FWHM） of the peak in DTG increased.

Synthesis and Evaluation on Performance of Hydrogen Storage of Multi-Walled Carbon Nanotubes Decorated with Platinum

By means of chemical reduction,nanoparticles of platinum were deposited on the surface of multi walled carbon nanotubes (MWCNTs).The performance of hydrogen storage of as prepared MWCNTs decorated with platinum was investigated.The results indicate that:(1) Hydrogen uptake is more quick and intense for decorated MWCNTs than that for not decorated ones at 10.931MPa and room temperature.The saturation of hydrogen uptake of the former only lasts about 30min,while the latter needs about 150 min;(2) The amount of hydrogen uptake of decorated MWCNTs is about 1.13wt%, which is larger than that of not decorated ones(about 0.54wt%);(3) However,more than 37% hydrogen absorbed by decorated MWCNTs is chemisorbed.

丙硫醇辅助合成石墨化碳载Pt纳米颗粒以提高燃料电池启停性能

石墨化碳作为质子交换膜燃料电池的阴极催化剂载体,虽然在增强催化剂抗腐蚀性方面具有显著优势,但由于其孔隙率低,缺乏缺陷结构,在石墨化碳载体上制备小尺寸Pt纳米颗粒依然面临挑战。本文报道了一种使用丙硫醇辅助浸渍法,来实现石墨化碳上Pt纳米颗粒的尺寸控制。研究表明,丙硫醇在浸渍过程中与Pt配位形成的配位络合物,在随后的热还原过程转化为硫掺杂碳涂层,从而保证了石墨化碳上小尺寸Pt纳米颗粒的合成。由于有效的尺寸控制,相比于传统浸渍法,此方法所制备的阴极催化剂具有更高的燃料电池性能。我们使用美国能源部(DOE)推荐的耐久性测试方案对所合成的催化剂进行了加速应力测试。在1.0–1.5 V电压区间循环5000圈后,所制备催化剂在1.5 A·cm^(-2)电流密度处的电压损失仅为10 mV,可以忽略不计,达到了DOE载体耐久性目标(30 mV)。

New Rh-ZnO/Carbon Nanotubes Catalyst for Methanol Synthesis

A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.

不同碳载体负载Pt催化剂ORR性能的研究

使用乙二醇还原法在不同的商业碳载体上制备了系列铂碳催化剂,考察了碳载体对铂基催化剂ORR性能的影响。结果表明,600JD-L是最佳载体,其相应催化剂LSV半波电位达0.89V,塔菲尔斜率为93.4 mVdec-1,质量比活性为239.8 mA/mgPt。

直接甲醇燃料电池中碳基载体材料的研究进展

甲醇氧化电催化剂是决定直接甲醇燃料电池(DMFCs)性能、寿命与成本的关键。为获得高功率密度和低生产成本的DMFCs,设计合成组成、结构、形貌可控的阳极催化剂备受关注。阳极催化剂的颗粒尺寸、粒径分布、形貌结构、稳定性、分散性以及催化活性都与载体息息相关,而碳基载体材料由于其优异的性能已广泛应用于DMFCs中。首先,介绍了酸性环境和碱性环境中甲醇氧化反应的机理;然后,对不同形式的碳基载体材料,如炭黑、介孔碳、碳纳米材料、氧功能化碳、杂原子掺杂碳以及金属氧化物改性碳作为催化剂载体在DMFCs中的应用进行了综述;最后,对DMFCs的发展趋势进行了展望。

碳纳米管表面修饰程度对碳纳米管载Pt电催化性能的影响

比较了用不同温度的浓HNO3处理的碳纳米管(CNTs)作载体的Pt(Pt/CNTs)对甲醇氧化的电催化活性.结果表明浓HNO3处理使CNTs表面修饰上的含氧基团对CNTs上沉积Pt粒子的平均粒径有较大影响.表面修饰程度适当时,制得的Pt/CNTs中Pt粒子较小,因此,对甲醇氧化的电催化活性较高.而表面修饰程度过大,易使Pt粒子团聚,从而降低Pt/CNTs催化剂对甲醇氧化的电化学活性.

碳纳米管结构对碳纳米管载Pt催化剂电催化性能的影响

在制备单、双壁及不同管径的多壁碳纳米管(CNTs)的基础上,用液相还原法把Pt沉积到单、双壁和管径不同的多壁CNTs上.发现制得的CNTs载Pt(Pt/CNTs)催化剂对甲醇氧化的电催化活性随CNTs管径减小而增加.这归结于管径小的CNTs的比表面积较大,含氧基团多,有利于提高Pt粒子分散度,加上管径小的单壁CNTs具有更高的导电性,这些因素都有利于提高Pt/CNTs催化剂对甲醇氧化的电催化活性.

Preparation of high active Pt/C cathode electrocatalyst for direct methanol fuel cell by citrate-stabilized method

Platinum nanoparticles supported on carbons（Pt/C,60%,mass fraction） electrocatalysts for direct methanol fuel cell（DMFC） were prepared by citrate-stabilized method with different reductants and carbon supports.The catalysts were characterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM） and cyclic voltammetry（CV）.It is found that the size of Pt nanoparticles on carbon is controllable by citrate addition and reductant optimization,and the form of carbon support has a great influence on electrocatalytic activity of catalysts.The citrate-stabilized Pt nanoparticles supported on BP2000 carbon,which was reduced by formaldehyde,exhibit the best performance with about 2 nm in diameter and 66.46 m2/g（Pt） in electrocatalytic active surface（EAS） area.Test on single DMFC with 60%（mass fraction） Pt/BP2000 as cathode electrocatalyst showed maximum power density at 78.8 mW/cm2.