Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

Effect of MnOx phase on Pt-based catalyst for enhancing CO/C3H6/NO oxidation performance

To improve the fuel economy, it is crucial to promote the low-temperature performance in eliminating diesel emissions. The work investigates the impact of different MnO₂/Mn₂O₃ phase ratio on the low-temperature performance of Pt-based monolithic diesel oxidation catalyst. Near equal ratio of MnO_x phase could form the three-phase (platinum, MnO₂, Mn₂O₃) interfacial structure, leading to the smaller platinum particle size and exhibiting the higher interface rate (1.6–11.1 times) than other mono-manganese oxide with platinum. Besides, the higher oxygen mobility and more active oxygen species could be contributed to the positive effect of Pt/MnO_x interface, which are prevalent to activate the reactant and greatly enhance the TOF value (1.4–20.8 times). The results imply that the modification of multi-phase metal/oxide interface is potential in dispersing platinum for greatly enhancing the catalytic efficiency.     

Effect of mesoporous carbon on oxygen reduction reaction activity as cathode catalyst support for proton exchange membrane fuel cell

In this paper, a new carbon support with a large number of mesoporous-structures is selected to prepare Pt/C catalysts. Transmission electron microscope (TEM) results show that the Pt/3# catalyst presents a sponge-like morphology, Pt particles are not only evenly distributed on the surface of carbon support, but also the smaller Pt particles are deposited in the mesoporous inside the support. The average diameter of Pt particles is only 2.8 nm. The membrane electrode assembly (MEA) based on Pt/3# catalyst also shows excellent performance. In conclusion, the 3# support is an idea carbon support for PEMFC, which helps to improve the oxygen reduction reaction (ORR) activity of the catalyst. Based on the “internal-Pt” structure of the support mesoporous, the efficient three-phase boundaries (TPBs) are construct to avoid the poisoning effect of ionomer on the nano-metal particles, reduce the activation impedance and oxygen mass transfer impedance, and improve the reaction efficiency.     

Pore-scale study of effects of different Pt loading reduction schemes on reactive transport processes in catalyst layers of proton exchange membrane fuel cells

Reducing the Platinum (Pt) loading while maintaining the performance is highly desired for promoting the commercial use of proton exchange membrane fuel cells (PEMFCs). Different methods have been adopted to fabricate catalyst layers (CLs) with low Pt loading, including utilizing lower Pt/C catalysts (MA), mixing high Pt/C catalysts with bare carbon black particles (MB), and reducing CL thickness while maintaining high Pt/C ratio (MC). In this study, self-developed pore-scale model is adopted to investigate the performance of the three Pt reduction methods. It is found that MA shows the best performance while MB shows the worst. Then, effects of Pt dispersion are further explored. The results show that denser Pt sites will result in higher local oxygen flux and thus higher local transport resistance. Therefore, MA method, which shows the better Pt dispersion, leads to improved performance. Third, CLs with quasi-realistic structures are investigated. Higher tortuosity resulting from the random pores produces higher bulk resistance along the thickness direction, while MA still exhibits the best performance. Finally, improved CL structures are investigated by designing perforated CL structures. It is found that adding perforations can significantly reduce the bulk transport resistance and can improve the CL performance. It is demonstrated that CL structure plays important roles on performance, and there are still huge potentials to further improve CL performance by increasing Pt dispersion and optimizing CL structures.     

Preparation of PEDOT-modified double-layered hollow carbon spheres as Pt catalyst support for methanol oxidation

In this paper, Pt nanoparticles (Pt NPs) deposited hybrid carbon support is prepared by modifying double-layered hollow carbon spheres（DLHCs）with poly(3,4-ethylenedioxythiophene) (PEDOT) and used as anode catalyst of methanol oxidation. The structure of nanocomposites is characterized by SEM, TEM, FT-IR, XRD and XPS, confirming the greatly enhanced synergistic effect between the PEDOT and DLHCs, and illustrating the uniform distribution of Pt NPs on the PEDOT/DLHCs composite surface with a small particle size (~2.63 nm). Cyclic voltammetry, chronoamperometry and impedance spectroscopy applied to determine the electrocatalytic activity of catalysts, it is found that the synthesized PEDOT/DLHCs/Pt possesses excellent characteristics such as large electrochemically active surface area and high mass activity of 59.45 m² g⁻¹ and 807 mA mg⁻¹ in 0.5 M H₂SO₄ containing 1 M methanol solution, which is almost 1.24 and 2.8 times greater than those of commercial Pt/C, and the catalyst exhibits superior stability after 500 durability cycles. The enhanced electrocatalytic behavior can be ascribed to the excellent electronic conductivity of PEDOT-modified DLHCs and the strong binding of PEDOT/DLHCs to Pt NPs, suggesting that the PEDOT/DLHCs/Pt is a promising electrocatalyst for direct methanol fuel cell.     

A highly active composite electrocatalyst Ni–Fe–P–Nb2O5/NF for overall water splitting

This work demonstrates a facile Nb₂O₅-decorated electrocatalyst to prepare cost-effective Ni–Fe–P–Nb₂O₅/NF and compared HER & OER performance in alkaline media. The prepared electrocatalyst presented an outstanding electrocatalytic performance towards hydrogen evolution reaction, which required a quite low overpotential of 39.05 mV at the current density of ?10 mA cm^?2 in 1 M KOH electrolyte. Moreover, the Ni–Fe–P–Nb₂O₅/NF catalyst also has excellent oxygen evolution efficiency, which needs only 322 mV to reach the current density of 50 mA cm^?2. Furthermore, its electrocatalytic performance towards overall water splitting worked as both cathode and anode achieved a quite low potential of 1.56 V (10 mA cm^?2).     

Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

钕铁硼化学镀防护及在模拟海洋大气环境中的腐蚀行为

采用化学镀方法在钕铁硼表面分别制备Ni-P合金镀层、Ni-Mo-P合金镀层、Ni-P/PTFE复合镀层和Ni-Mo-P/PTFE复合镀层,并研究了不同化学镀层在模拟海洋大气环境中的腐蚀行为。结果表明:Ni-P合金镀层、Ni-Mo-P合金镀层、Ni-P/PTFE复合镀层和Ni-Mo-P/PTFE复合镀层都完整覆盖钕铁硼表面,它们的粗糙度差别不大,在模拟海洋大气环境中的腐蚀失重都低于钕铁硼的腐蚀失重,容抗弧半径增大且电荷转移电阻有不同程度的提高。与Ni-P合金镀层和Ni-Mo-P合金镀层相比,Ni-P/PTFE复合镀层和Ni-Mo-P/PTFE复合镀层具有优良的耐腐蚀性能,原因在于PTFE颗粒较均匀的沉积在镀层表面增加一道屏蔽层,也起到阻碍腐蚀介质渗透腐蚀的作用。尤其是Ni-Mo-P/PTFE复合镀层,其表面更致密,PTFE颗粒沉积更均匀,能更有效延缓腐蚀介质与钕铁硼接触,显著提高钕铁硼在模拟海洋大气环境中的耐腐蚀性能。     

镀液温度实时控制系统的设计与实现

针对镀液温度变化的非线性和滞后性,设计了采用专家规则的镀液温度实时控制系统。该系统在实时监测的基础上,构建了综合评判镀液温度偏差和镀液温度偏差变化率的专家规则,实现了镀液温度的自适应快速调节。仿真分析结果表明,该系统克服了非线性和滞后性的不良影响,能够实现镀液温度的实时控制。     

负载型Pt-Fe/SiO_2催化剂催化环己烷一步氧化制己二酸

己二酸是合成尼龙-66和尼龙-46纤维的重要原料,并进一步用于生产许多重要的化工产品。工业上的己二酸多采用以硝酸为氧化剂的两步法合成,该工艺不仅工艺复杂,而且对设备有腐蚀作用,还会释放大量的温室气体N_2O。本文以负载型Pt/SiO_2、Fe/SiO_2和Pt-Fe/SiO_2为催化剂,采用过氧化氢和氧气为氧源,研究了环己烷一步氧化制己二酸的绿色合成路线。对催化剂进行ICP、BET比表面积、XRD、TEM等表征,结果表明,Pt-Fe/SiO_2催化剂中不存在与Pt或Fe对应的衍射峰。在最佳反应条件下,用高压釜进行了催化剂性能评价,结果表明,Pt-Fe/SiO_2催化活性略优于Pt/SiO_2和Fe/SiO_2。在环己烷转化率为28%的情况下,己二酸选择性达到33%。