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.     

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.     

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.     

The significant promotion of g-C3N4 on Pt/CNS catalyst for the electrocatalytic oxidation of methanol

This article reported a series of g–C₃N₄–CNS (g-C₃N₄ and carbon nanosheets) composite carriers formed by the hydrothermal method, and then the ethylene glycol reduction method was used to anchor Pt nanoparticles on the g–C₃N₄–CNS carrier to form the Pt/g–C₃N₄–CNS catalysts. The electrochemical test for the electrocatalytic oxidation of methanol (MOR) shown that the Pt/20%g–C₃N₄–CNS catalyst has the best catalytic performance and stability. These Pt/g–C₃N₄–CNS catalysts were analyzed by TEM, XRD, XPS, and BET characterization. It is discovered that the amount of g-C₃N₄ greatly influenced the structure and chemical properties of Pt/CNS precursor. As the content of g-C₃N₄ increases, the content of pyridine nitrogen and pyrrole nitrogen also increases, and N species can enhance the interaction between Pt nanoparticles and CNS, promote Pt dispersion, and increase the specific surface area of the catalyst. Similarly, an excessive addition of g-C₃N₄ will cause a sharp decline in the conductivity of the catalyst, and then led to the decline of MOR activity.     

Pt–Ru nanoparticles anchored on poly(brilliant cresyl blue) as a new polymeric support: Application as an efficient electrocatalyst in methanol oxidation reaction

The glassy carbon electrode is modified by poly(brilliant cresyl blue) (PBCB) to be applied as a new green and efficient platform for Pt and Pt–Ru alloy nanoparticles deposition. Surface composition, morphology and catalytic activity of these modified electrodes towards methanol oxidation are assessed by applying X-ray diffraction, field emission scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques. The X-ray diffraction patterns reveal that the highly crystalline Pt and Pt–Ru alloy and RuO₂ nanoparticles with low crystallinity are deposited on the PBCB modified glassy carbon electrodes. The microscopic images indicate smaller size and better distribution of deposited nanoparticles on the surface of PBCB modified electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy results reveal that PBCB supported Pt and Pt–Ru nanoparticles have better electrocatalytic performance and durability towards methanol oxidation rather than the unsupported nanoparticles. From the obtained results it can be concluded that the presence of PBCB not only improves the stability of nanoparticles on the surface, but also leads to the formation of smaller size and more uniform distribution of nanoparticles on the surface, which, in turn, cause the nanoparticles to provide a higher accessible surface area and more active centers for the oxidation of methanol. The results will be valuable in extending the applications of this polymer in surface modification steps and in developing promising catalyst supports to be applied in direct methanol fuel cells.     

Anchoring single Pt atoms on hollow Ag3VO4 spheres for improved activity towards photocatalytic H2 evolution reaction

The high cost of noble metal catalysts has been a great bottleneck for the catalyst industry. Using the noble metal at a single-atom level for catalytic applications could dramatically decrease the cost. The impacts of single Pt atoms on the photocatalytic performance of Ag₃VO₄ have been investigated and reported. In this report, single Pt atoms were anchored on the surface of Ag₃VO₄ (AVO) as a cocatalyst, and the resultant composite photocatalyst has been studied for photocatalytic H₂ production from water driven by visible light. The as-prepared AVO particles are hollow nanospheres in the monoclinic phase with a bandgap of 2.20 eV. The light absorption edge of AVO/Pt is slightly red-shifted compared to that of the pristine AVO, indicating more visible light absorption of AVO/Pt. The XPS peaks of Ag, V, and Pt exhibit a significant shift after AVO and Pt get into contact, suggesting the strong interaction between the surface Ag and V atoms, and single Pt atoms. After 3-h illumination, the photocatalytic H₂ evolution amount from AVO/Pt is improved up to 1400 μmol, which is 2.8 times that on the bare AVO. Such efficient photocatalytic H₂ evolution on AVO/Pt is still maintained after five reaction cycles. The better photocatalytic performance of AVO/Pt has been attributed to the more efficient visible light utilization and the lower interfacial charge transfer resistance, as demonstrated in the DRS and EIS spectra. The presence of the surface Pt atoms also leads to a higher amount of reactive radicals, which could efficiently promote the surface redox reactions.     

高分散度Pt/C电催化剂的制备

Cabot公司Vulcan XC-72型炭黑，经过H2O2氧化处理后作为Pt的载体，H2PtCl6作为金属前驱体制备了高度分散的Pt/C催化剂。讨论了不同条件下H2PtCl6在炭黑上的吸附性能。载体经过H2O2氧化处理24h,H2PtCl6在pH=9下吸收48h，H2 350℃还原2h，可以制备出铂晶粒平均大小为1.8nm的Pt/C电催化剂。     

Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

Selectivity Enhancement to the Exclusive Formation of Ethyltoluenes and Hydrogen During Dehydroalkylation of Toluene with Ethane

The dehydroalkylation of toluene with ethane to the isomeric ethyltoluenes was studied on 0.4Pt/H-ZSM-5 at varying contact times (1/WHSV). At a high contact time of 1.0 h, toluene disproportionation and hydrogenolysis reactions dominate, resulting in low selectivity to the desired ethyltoluenes via the alkylation reaction. However, at a low contact time of 0.12 h side reactions are eliminated, resulting in maximum selectivities to the kinetically favored ethyltoluenes and hydrogen. Results at high selectivities to ethyltoluenes provide significant insight into reaction pathways.     

Catalytic oxidation of naphthalene using a Pt/Al2O3 catalyst

Polycylic aromatic hydrocarbons (PAHs) are listed as carcinogenic and mutagenic priority pollutants, belonging to the environmental endocrine disrupters. Most PAHs in the environment stem from the atmospheric deposition and diesel emission. Consequently, the elimination of PAHs in the off-gases is one of the priority and emerging challenges. Catalytic oxidation has been widely used in the destruction of organic compounds due to its high efficiency (or conversion of reactants), its economic benefits and good applicability.

This study investigates the application of the catalytic oxidation using Pt/γ-Al₂O₃ catalysts to decompose PAHs and taking naphthalene (the simplest and least toxic PAH) as a target compound. It studies the relationships between conversion, operating parameters and relevant factors such as treatment temperatures, catalyst sizes and space velocities. Also, a related reaction kinetic expression is proposed to provide a simplified expression of the relevant kinetic parameters.

The results indicate that the Pt/γ-Al₂O₃ catalyst used accelerates the reaction rate of the decomposition of naphthalene and decreases the reaction temperature. A high conversion (over 95%) can be achieved at a moderate reaction temperature of 480 K and space velocity below 35,000 h⁻¹. Non-catalytic (thermal) oxidation achieves the same conversion at a temperature beyond 1000 K. The results also indicate that Rideal–Eley mechanism and Arrhenius equation can be reasonably applied to describe the data by using the pseudo-first-order reaction kinetic equation with activation energy of 149.97 kJ/mol and frequency factor equal to 3.26 × 10¹⁷ s⁻¹.