On the preparation methods for carbon nanofiber-supported Pt catalysts

A study of the suitability of different methods for preparing highly loaded, well dispersed carbon nanofiber (CNF) supported Pt catalysts intended for application in fuel cells is reported. Preparation routes that are successfully applied on conventional carbon supports are hampered by the lower surface area and number of surface groups on CNFs. Ion exchange, homogeneous deposition precipitation and impregnation are all techniques that are limited to low metal loading on this CNF support. The most promising methods are the colloidal methods. By the modified polyol method, a Pt-content of 24 wt% with a particle size of 2–4 nm was achieved. CNFs could also be completely covered by 2–3 nm Pt oxide particles by using the metal–oxide colloid route, reaching a Pt-content of 17 wt%. The merits that make these methods more suitable than the other methods and the mechanism for deposition of Pt particles on CNFs are discussed.     

Fabrication of CNTs with controlled diameters and their applications as electrocatalyst supports for DMFC

A facile synthesis procedure based on chemical vapor deposition (CVD) process has been developed to fabricate carbon nanotubes (CNTs) with controlled diameters and high yields utilizing Fe-containing ordered hexagonal mesoporous silicas (HMSs) such as MCM-41 and SBA-15 having varied pore sizes as the catalysts as well as the templates. It is found that unlike Fe/HMS catalysts prepared by co-precipitation method, samples prepared by the impregnation method gave rise to multi-wall CNTs with uniform diameters, which were largely dictated by the pore size of the Fe/HMS catalysts. Among these uniform MWCNTs, sample with a larger diameter (≥ 8 nm) was found to be more favorable as support for Pt catalyst, leading to a homogeneous dispersion of metal nanoparticles. Consequently, the Pt/CNT electrocatalysts so prepared gave rise to superior methanol oxidation activities as well as tolerances for CO poisoning compared to Pt supported on commercial single-wall CNT (Pt/SWCNT) and XC-72 activated carbon (Pt/XC-72) having a similar metal loading.     

Highly dispersed Pt nanoparticles by pentagon defects introduced in bamboo-shaped carbon nanotube support and their enhanced catalytic activity on methanol oxidation

Bamboo-shaped carbon nanotubes (BCNTs), which were synthesized through chemical vapor deposition by using cresol as the carbon source, were explored as Pt catalyst support in comparison with conventional carbon nanotubes (CNTs) and Vulcan XC carbon blacks. The pyrolysis of cresol produced a large amount of pentagon defects introduced in the walls of BCNTs, which could possess higher chemical activity and stronger interaction with metal particles. After a mild purification, the BCNTs exhibited more oxygen-containing functional groups than CNTs, as shown by Fourier transform infrared spectra and cyclic voltammetry. The formed oxygen-containing functional groups as well as the pentagon defects could act as uniform active sites for metal particle loading. By ethylene glycol reduction, highly dispersed Pt nanoparticles with a narrow size distribution of 2-3 nm were easily supported on BCNTs, as shown by transmission electron microscope. The Pt/BCNT catalyst showed higher electro-catalytic activity on the methanol oxidation than the Pt/CNT and Pt/Vulcan XC catalyst, which could be largely ascribed to the highly dispersed Pt nanoparticles due to the introduced pentagon defects in the tube-walls (comparing with Pt/CNT) and the graphitic nanotube network that could provide good electron conduction (comparing with Pt/Vulcan XC).     

Influence of Pyridine‐Polybenzimidazole Film Thickness of Carbon Nanotube Supported Platinum on Fuel Cell Applications

Pyridine‐polybenzimidazole (PyPBI) films of different thickness (∼1.0–2.4 nm) are wrapped on the surfaces of multi‐walled carbon nanotubes (CNTs). To prepare Pt on PyPBI/CNT (Pt‐PyPBI/CNT) catalysts, Pt⁴⁺ ions are immobilized on these PyPBI wrapped CNTs (PyPBI/CNTs) via Lewis acid‐base coordination between Pt⁴⁺ and :N‐ of imidazole groups, followed by reducing Pt⁴⁺ to Pt nanoparticles. The influence of PyPBI film thickness on the Pt particle size, loading and electrochemical surface area, respectively, of Pt‐PyPBI/CNTs is investigated. Fuel cell performances of the PBI/H₃PO₄ based membrane electrode assemblies (MEAs) prepared from these Pt‐PyPBI/CNT catalysts are also evaluated at 160 °C with unhumidified H₂/O₂ gases. Among the catalysts, the Pt‐PyPBI/CNT catalyst with a PyPBI film thickness of ∼1.6 nm (which is around half of the Pt particle size), a Pt loading of ∼44 wt.%, and a Pt particle size of ∼3.3 nm exhibits the best fuel cell performance.     

Activity,selectivity, and methanol tolerance of novel carbon-supported Pt and Pt<Subscript>3</Subscript>Me (Me = Ni,Co) cathode catalysts

The activity, selectivity, and methanol tolerance of novel, carbon supported high-metal loading (40 wt.%) Pt/C and Pt₃Me/C (Me = Ni, Co) catalysts for the O₂ reduction reaction (ORR) were evaluated in model studies under defined mass transport and diffusion conditions, by rotating (ring) disk and by differential electrochemical mass spectrometry. The catalysts were synthesized by the organometallic route, via deposition of pre-formed Pt and Pt₃Me pre-cursors followed by their decomposition into metal nanoparticles. Characteristic properties such as particle sizes, particle composition and phase formation, and active surface area, were determined by transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. For comparison, commercial Pt/C catalysts (20 and 40 wt.%, E-Tek, Somerset, NJ, USA) were investigated as well, allowing to evaluate Pt loading effects and, by comparison with the pre-cursor-based catalyst with their much smaller particle sizes (1.7 nm diameter), also particle size effects. Kinetic parameters for the ORR were evaluated; the ORR activities of the bimetallic catalysts and of the synthesized Pt/C catalyst were comparable and similar to that of the high-loading commercial Pt/C catalyst; at typical cathode operation potentials H₂O₂ formation is negligible for the synthesized catalysts. Due to their lower methanol oxidation activity the bimetallic catalysts show an improved methanol tolerance compared to the commercial Pt/C catalysts. The results indicate that the use of very small particle sizes is a possible way to achieve reasonably good ORR activities at an improved methanol tolerance at DMFC cathode relevant conditions.     

Morphology‐dependent electrocatalytic activity of nanostructured Pt/C particles from hybrid aerosol–colloid process

An optimum nanostructure and pore size of catalyst supports is very important in achieving high catalytic performances. In this instance, we evaluated the effects of various carbon nanostructures on the catalytic performances of carbon‐supported platinum (Pt/C) electrocatalysts experimentally and numerically. The Pt/C catalysts were prepared using a hybrid method involving the preparation of dense, hollow, and porous nanostructured carbon particle via aerosol spray pyrolysis followed by microwave‐assisted Pt deposition. Electrochemical characterization of the catalysts showed that the porous Pt/C catalyst gave the best performance; its electrochemical surface area was much higher, more than twice than those of hollow or dense Pt/C. The effects of pore size on electrocatalysis were also studied. The results showed the importance of a balance between mesopores and macropores for effective catalysis with a high charge transfer rate. A fluid flow model showed that good oxygen transport contributed to the catalytic activity. © 2015 American Institute of Chemical Engineers AIChE J, 62: 440–450, 2016     

炭载体前处理对Pt-Ru/C催化剂性能影响

为研究水蒸气处理后热处理对炭黑表面特性的影响,提高DMFC阳极催化剂的催化活性,利用先水蒸气处理后热处理的Vnlcan XC-72炭黑为载体制备Pt-Ru/C催化剂,与水蒸气处理的和未经处理的炭载体制备Pt-Ru/C催化剂的性能进行比较.采用XPS和BET测试了处理后的炭粉表面的含氧浓度和比表面,结果表明：水蒸气处理后,炭载体比表面积增大,含氧浓度降低;水蒸气处理后热处理,炭载体比表面积进一步减小,含氧浓度增加.用XRD对催化剂的结构进行了表征,结果表明：水蒸气处理后热处理的炭黑为载体制备Pt-Ru/C催化剂结晶状态良好,催化剂颗粒较小.在0.5mol/L CH3OH和0.5mol/L H2SO4混合溶液中,利用玻炭电极测试了循环伏安曲线和阶跃电位曲线,结果表明：用先水蒸气处理后热处理的炭粉为载体制备的催化剂比仅水蒸气处理和未经处理的炭粉为载体制备的催化剂的活性最高.     

Increased Metal Utilization in Carbon‐Supported Pt Catalysts by Adsorption of Preformed Pt Nanoparticles on Colloidal Silica

Pt/C electrocatalysts, aimed at maximizing the electrochemical surface area (ECSA) and consequently the specific mass activity of fuel cell reactions, are obtained by firstly depositing Pt nanoparticles on colloidal silica (Pt‐silica), followed by the adsorption of the latter onto a carbon support. This method of catalyst preparation increases Pt metal utilization and generates accessible void space in the interpenetrating particle network of carbon and silica for the facile transport of reactants and products. Both electrochemical hydrogen adsorption/desorption and CO oxidation measurements show an increase in the ECSA using this approach. Methanol electrooxidation is used as a test reaction to evaluate the catalytic activity. It is found that the silica modified catalyst is three times as active as a catalyst prepared without silica, under otherwise identical conditions.     

The effect of the Pt deposition method and the support on Pt dispersion on carbon nanotubes

Carbon nanotube supported platinum (Pt/CNTs) catalysts prepared by different Pt deposition methods and on different CNT supports were studied. Colloidal based methods were demonstrated to be more effective than other wet chemistry deposition methods (e.g., impregnation and precipitation) for the preparation of highly dispersed Pt/CNTs. Pt catalyst supported on CNTs with a dispersion uniformity comparable to that supported on carbon powder was achieved using a zwitterionic surfactant 3-(N,N-dimethyldodecylammonio) propanesulfonate (SB12) as stabilizer in a monitored pH environment. It was experimentally observed that oxygen-containing surface functionalities on CNTs can greatly affect the catalyst particle dispersion by manipulating Pt anchoring and/or nucleating sites. Furthermore, it was revealed that the performance of Pt/CNTs based fuel cell is strongly dependent on the electrode fabrication method.     

Synthesis and electro-catalytic activity of methanol oxidation on nitrogen containing carbon nanotubes supported Pt electrodes

Template synthesis of various nitrogen containing carbon nanotubes using different nitrogen containing polymers and the variation of nitrogen content in carbon nanotube (CNT) on the behaviour of supported Pt electrodes in the anodic oxidation of methanol in direct methanol fuel cells was investigated. Characterizations of the as-prepared catalysts are investigated by electron microscopy and electrochemical analysis. The catalyst with N-containing CNT as a support exhibits a higher catalytic activity than that carbon supported platinum electrode and CNT supported electrodes. The N-containing CNT supported electrodes with 10.5% nitrogen content show a higher catalytic activity compared to other N-CNT supported electrodes. This could be due to the existence of additional active sites on the surface of the N-containing CNT supported electrodes, which favours better dispersion of Pt particles. Also, the strong metal-support interaction plays a major role in enhancing the catalytic activity for methanol oxidation.     

Reducibility of Platinum Supported on Nanostructured Carbons

The nanostructure of graphite like carbon, i.e. carbon nanofibers (CNF), carbon nanotubes (CNT) and carbon nanoplatelets (CNP), displayed a significant influence on the reducibility of platinum deposited on these carbons. The onset temperature for reduction increased from 461 K for Pt/CNF to 466 K for Pt/CNP and 487 K for Pt/CNT. The retarded reduction for Pt/CNT was related to the higher amount of acidic oxygen surface groups on this support resulting in a strong stabilization of the cationic platinum species. A higher reduction temperature for that sample increased the amount of metallic platinum, however the platinum particle size was larger (2–11 nm) compared to that of Pt/CNF and Pt/CNP (both 1–3 nm). The orientation of the graphene sheets had a significant influence on the selectivity for cinnamaldehyde hydrogenation: Pt/CNP resulted in a higher selectivity towards cinnamyl alcohol compared to Pt/CNF.     

Chemical vapor deposition of highly dispersed Pt nanoparticles on multi-walled carbon nanotubes for use as fuel-cell electrodes

Fuel-cell electrode catalysts with improved electrochemical properties have been prepared by dispersing Pt nanoparticles onto carbon nanotubes (CNT) using a chemical vapor deposition (CVD) method. (Trimethyl)methylcyclopentadienyl platinum (MeCpPtMe₃) has been used as a Pt precursor in the CVD process and the CVD conditions have been optimized to disperse small Pt particles onto the CNT. Pt particles synthesized by CVD have a relatively uniform size of approximately 1 nm, which is substantially smaller than in the case of a commercial Pt/carbon black catalyst (?4.5 nm) prepared by wet impregnation. The dispersion of Pt, estimated by CO chemisorption, is also more than 14% greater than the commercial catalyst with these smaller particles. The electrochemically active surface area (ESA), measured by cyclic voltammetry (CV), and the long-time durability of the surface area of Pt/CNT prepared by CVD are higher than those of the commercial catalyst. Consequently, the single cell performance of the former catalyst is superior to that of the latter one.     

Synthesis of an improved hierarchical carbon-fiber composite as a catalyst support for platinum and its application in electrocatalysis

A hierarchical carbon-fiber composite was synthesized based on carbon cloth (CC) modified with primary carbon microfibers (CMF) and subsequently secondary carbon nanotubes (CNT), thus forming a three-dimensional hierarchical structure with high BET surface area. The primary CMFs and the secondary CNTs are grown with electrodeposited iron nanoparticles as catalysts from methane and ethylene, respectively. After deposition of Pt nanoparticles by chemical vapor deposition from (trimethyl)cyclopentadienylplatinum, the resulting hierarchical composite was used as catalyst in the electrocatalytic oxygen reduction (oxygen reduction reaction, ORR) as specific test reaction. The modification of the CC with CMFs and CNTs improved the electrochemical properties of the carbon composite as revealed by electrochemical impedance measurements evidencing a low charge transfer resistance for redox mediators at the modified CC. X-ray photoelectron spectroscopy measurements were carried out to identify the chemical state and the surface atomic concentration of the Pt catalysts deposited on the hierarchical carbon composites. The ORR activity of Pt supported on different composites was investigated using rotating disk electrode measurements and scanning electrochemical microscopy. These electrochemical studies revealed that the obtained structured catalyst support is very promising for electrochemical applications, e.g. fuel cells.     

Palladium and platinum catalysts supported on carbon nanofiber coated monoliths for low-temperature combustion of BTX

In this work carbon nanofiber (CNF)-coated monoliths with a very thin, homogeneous, consistent and good adhered CNF layer were obtained by means of catalytic decomposition of ethylene on Ni particles.The catalytic behaviour of Pt and Pd supported on the CNF-coated monoliths was studied in the low-temperature catalytic combustion of benzene, toluene and m-xylene (BTX) and compared with the performance of Pt and Pd supported on γ-Al₂O₃ coated monoliths.The catalysts supported on CNF-coated monoliths were the most active, independent of the metal catalyst or the type of the tested aromatic compound. TPD experiments showed that the γ-Al₂O₃ phase retained important amounts of the water molecules produced during the reaction. When water vapour was supplied to the reactant flow, the activity of Pd catalysts decreased much stronger than the Pt ones, and the activity of the Pt catalysts supported on the γ-Al₂O₃ was more affected than that of the catalysts supported on CNF.BTX combustion reactions seem to be catalyzed by Pt and Pd through different kinetic mechanisms, explaining why Pt catalysts always were more active than the Pd ones deposited on the same type of support. Pd catalyzed combustion of benzene is strongly inhibited by oxygen and by water.Catalysts supported on CNF-coated monoliths showed a selectivity to burn benzene better than toluene or m-xylene, attributed to a better aromatic-CNF surface interaction.     

Synthesis of OMC supported Pt catalysts and the effect of the metal loading technique on their PEM fuel cell performances

Abstract

Ordered mesoporous carbon (OMC) supported Pt catalysts were prepared by different loading techniques, in order to be used in the catalysis of oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells. OMC was synthesized by an organic-inorganic self assembly route using Pluronic F127 as surface directing agent, resorcinol-formaldehyde as carbon source and tetraethyl ortosilicate (TEOS) as silica source. Pt loading was achieved by three different approaches; one pot in situ synthesis, wet impregnation and surface-modified wet impregnation. Nitrogen adsorption studies showed slight reductions in surface areas, which can be attributed to partial losses of micropore volumes. The XRD and TEM analysis revealed a better metal distribution and smaller particle size in the surface-modified sample with a mean Pt particle size of 3.83?nm. The modified sample also gave the most promising performance among the catalysts with a maximum power density of 73?mW cm^?2, which was very close to the commercial Pt/C catalyst.     

负载途径对炭气凝胶载Pt催化剂性能的影响

选择孔隙率高、孔隙尺寸小、比表面积大、电导率高、孔径大小及分布可控的新型炭材料炭气凝胶(CAs)为载体,通过在成品CAs表面负载和在CAs制备过程中同步负载两种途径制备了CAs负载的Pt催化剂,利用XRD、TEM、ICP及电化学循环伏安测试等手段对比讨论了负载途径对CAs载Pt催化剂物化性能及甲醇氧化催化活性的影响。结果表明,同步负载虽然可以简化制备工艺,但所制得的催化剂样品中催化活性组分Pt颗粒大、团聚严重、分散性差、负载量低,而且有许多Pt颗粒被包裹在CAs内部,因而导致了催化剂的有效利用率和催化性能降低。相反,通过在成品CAs表面负载的方法可以制得Pt颗粒小、分散均匀、实际负载量接近理论设计的高性能催化剂。     

Effects of carbon support on microwave-assisted catalytic dehydrogenation of decalin

Five types of carbon materials, including carbon nanotubes (CNTs), carbon nanofibres, carbon black, activated carbon and graphite, were evaluated in searching for an appropriate support for a Pt catalyst used for the dehydrogenation of decalin under microwave irradiation (MW). The thermal behaviour of different carbon materials and supported Pt catalysts suspended in decalin under MW was investigated. The dielectric properties and electrical conductivities of the carbon- and catalyst-containing decalin suspensions were measured and correlated with the thermal behaviour of the corresponding samples. Structural and textural characterisation was carried out to interpret the differences between the electrical conductivity of different samples. The catalytic performance of the Pt catalysts supported on different carbon materials was assessed to determine the catalysts’ ability to release H₂ during decalin dehydrogenation under MW. The results show that CNTs are the most suitable catalyst support because they exhibit the best thermal behaviour under MW and can provide a relatively large surface area for dispersing Pt nanoparticles. The high aspect ratio and low bulk density of CNTs gives rise to high electrical conductivity and, consequently, the large dielectric loss displayed by CNT-containing suspension, causing the outstanding thermal behaviour of CNT-containing suspension under MW.     

Catalytic ozonation of dimethyl phthalate with RuO2/Al2O3 catalysts prepared by microwave irradiation

Ruthenium catalysts supported on alumina were synthesized by microwave irradiation and used to catalyze ozonation of dimethyl phthalate in water. The catalysts enhanced greatly the TOC (total organic carbon) removal. The contribution of catalysis and adsorption to the overall TOC removal were 33% and 50%, respectively. 300 W was the optimal irradiation power for catalyst preparation. Moisture content had little effect on the catalytic activity. Compared to conventional irradiation, microwave irradiation benefited the catalytic activity because it provided a homogeneous dispersion of metal on the support. It is a promising thermal treatment method for developing the catalysts used in catalytic ozonation.     

Cobalt supported on carbon nanotubes — A promising novel Fischer–Tropsch synthesis catalyst

An extensive study of Fischer–Tropsch synthesis (FTS) on carbon nanotubes (CNT) supported and γ–alumina-supported cobalt catalysts with different amounts of cobalt are reported. Up to 40 wt.% of cobalt is added to the supports by the impregnation method. The effect of the support on the reducibility of the cobalt oxide species, dispersion of the cobalt, average cobalt clusters size, water–gas shift (WGS) activity and activity and selectivity of FTS is investigated. Using carbon nanotubes as cobalt catalyst support was found to cause the reduction temperature of cobalt oxide species to shift to lower temperatures. The strong metal-support interactions are reduced to a large extent and the reducibility of the catalysts improved significantly. CNT aided in well dispersion of metal clusters and average cobalt clusters size decreased. Results are presented showing that the hydrocarbon yield obtained by inventive CNT supported cobalt catalyst is surprisingly much larger than that obtained from cobalt on alumina supports. The maximum concentration of active surface Co° sites and FTS activity for alumina and CNT supported catalysts are achieved at 34 wt.% and 40 wt.% cobalt loading respectively. CNT caused a slight decrease in the FTS product distribution to lower molecular weight hydrocarbons.     

Hydrogenation of carbon dioxide over metal catalysts prepared using microemulsion

This paper relates to a novel preparation method of metal supported catalysts using microemulsions. The size distribution of metal particles in the catalysts, thus, prepared was appreciably narrow and the average particle size was much smaller than that of the conventional catalyst prepared from impregnation. It was found that the particle size could be controlled by the conditions of microemulsions regardless of metal content. The Rh, Pd and Pt catalysts prepared from microemulsions were found to exhibit a much higher activity for the hydrogenation of carbon dioxide than those from impregnation.