Structure-dependent activity and stability of Al2O3 supported Rh catalysts for the steam reforming of n-dodecane

Steam reforming of liquid hydrocarbon fuels is an appealing way for the production of hydrogen. In this work, the Rh/Al₂O₃ catalysts with nanorod (NR), nanofiber (NF) and sponge-shaped (SP) alumina supports were successfully designed for the steam reforming of n-dodecane as a surrogate compound for diesel/jet fuels. The catalysts before and after reaction were well characterized by using ICP, XRD, N₂ adsorption, TEM, HAADF-STEM, H₂-TPR, CO chemisorption, NH₃-TPD, CO₂-TPD, XPS, Al²⁷ NMR and TG. The results confirmed that the dispersion and surface structure of Rh species is quite dependent on the enclosed various morphologies. Rh/Al₂O₃-NR possesses highly dispersed, uniform and accessible Rh particles with the highest percentage of surface electron deficient Rh⁰ active species, which due to the unique properties of Al₂O₃ nanorod including high crystallinity, relatively large alumina particle size, thermal stability, and large pore volume and size. As a consequent, Rh/Al₂O₃-NR catalyst exhibited superior catalytic activity towards steam reforming reactions and hydrogen production rate over other two catalysts. Especially, Rh/Al₂O₃-NR catalyst showed the highest hydrogen production rate of 87,600 mmol g_fuel^?1 g_Rh^?1min^?1 among any Rh-based catalysts and other noble metal-based catalysts to date. After long-term reaction, a significant deactivation occurred on Rh/Al₂O₃–NF and Rh/Al₂O₃-SP catalysts, due to aggregation and sintering of Rh metal particles, coke deposition and poor hydrothermal stability of nanofibrous structure. In contrast, the Rh/Al₂O₃-NR catalyst shows excellent reforming stability with negligible coke formation. No significantly sintering and aggregation of the Rh particles is observed after long-term reaction. Such great catalyst stability can be explained by the role of hydrothermal stable nanorod alumina support, which not only provides a unique environment for the stabilization of uniform and small-size Rh particles but also affords strong surface basic sites.     

Cu-template-dependent synthesis of PtCu nanotubes for oxygen reduction reactions

The development of electrocatalysts with high activity and durability for oxygen reduction reaction (ORR) in acidic electrolyte environments remains a serious challenge for clean and efficient energy conversion. Synergistic effects between Pt and inexpensive metals, the d band center of Pt and catalyst morphology could adjust the adsorption and desorption of oxygen intermediates by the Pt. All the factors affect the catalytic performance of Pt-based nanocrystals. Here, we prepared Cu@PtCu₃ NWs with an average diameter of 74.9 nm for Cu and about 10 nm PtCu₃ layer. After etching, the Cu@PtCu₃ nanowires is transformed into PtCu nanotube structure, due to the removal of copper from the surface and interior. PtCu NTs for ORR shows excellent activities and durability due to the integration of structural advantages and synergistic effects. Notably, the mass activity and specific activity of PtCu NTs (0.105 A mg^?1_Pt and 0.230 mA cm^?2_Pt) are 2.0 and 3.8 times higher than that of commercial Pt/C (0.053 A mg^?1_Pt and 0.06 mA cm^?2_Pt). The etching process to change the morphology of the catalyst and alter the electronic structure of the catalyst is expected to be useful for the design of future structured Pt-based alloy nanocatalysts.     

Alkylated lignin with graft copolymerization for enhancing toughness of PLA

Journal of Materials Science - A green modification method for effectively enhancing toughness of PLA was established. Herein, alkaline lignin (LG) was firstly alkylated with dodecane, and then...     

Analysis and proposition of limiting current density measurement protocol

Limiting current density at different temperatures, backpressures, and balance gases can be used to separate molecular diffusion resistance, Knudsen diffusion resistance and local transport resistance of membrane electrode assembly (MEA). However, the measurement of limiting current density has no unified protocol. The diverse choices in the literature, either in the control of current or voltage or in the atmosphere like relative humidity and O₂ concentrations, make it difficult to compare the results and identify the true bottleneck hindering the mass transport. In this work, the current-voltage curves obtained by current scanning/stepping and voltage scanning/stepping methods under dilute O₂ of different concentrations and a wide range of relative humidity were measured and analyzed systematically. It is found that the voltage stepping method is superior to the other three ways of control for the reliable determination of the limiting current density. Aided with simultaneous electrochemical impedance spectroscopy measurement, the limiting current density can be determined with pinpoint accuracy. When the limiting current density is just used to qualitatively evaluate different MEA, the voltage scanning method can be used instead for its high time efficiency. The selection of the atmosphere also plays an important role in suppressing the distortion from excessive water and reducing the spurious contribution from proton conduction resistance. It is found that O₂ concentrations at 0.5 vol% and relative humidity at 90% can give the best estimation of O₂ transport resistance in membrane electrode assembly.     

Thiol-Functionalized Covalent Organic Frameworks as Thermal History Indictor for Temperature and Time History Monitoring

Various products, including foods and pharmaceuticals, are sensitive to temperature fluctuations. Thus, temperature monitoring during production, transportation, and storage is critical. Facile indicators are required to monitor temperature conditions via color changes in real time. This study aimed to prepare and apply thiol-functionalized covalent organic frameworks (COFs) as a novel indicator for monitoring thermal history and temperature abuse. The COFs underwent obvious color changes from bright yellow to purple after exposure to different temperatures for varying durations. The reaction kinetics are analyzed under isothermal conditions, which reveal that the order of reaction rates is k_−20°C < k_4°C < k_20°C < k_35°C < k_55°C. The activation energy (E_a) of the COFs is calculated using the Arrhenius equation as 50.71 kJ moL⁻¹. The COFs are capable of sensitive color changes and offer a broad temperature tracking range, thereby demonstrating their application potential for the monitoring of temperature and time exposure history during production, transportation, and storage. This excellent performance thermal history indicator also shows promise for expanding the application field of COFs.     

Microstructure and coloring mechanism of iron spots on bluish white porcelain from Jingdezhen of the Song Dynasty

Jingdezhen is famous for its bluish white (Qingbai) porcelains of the Song Dynasty, and those decorated with iron spots are distinctive among them. Herein, iron spots on a bluish white porcelain were investigated using a series of microscopic and spectroscopic characterizations. We found the decreasing iron content from more than 8 wt% to about 2 wt% during the glaze color transition from rusty to brown and finally into green, which built a connection on the coloring mechanism of iron-rich crystallized glaze and celadon glaze. We identified the rare ε-Fe₂O₃, a promising magnetic material, in both the dark brown crystals and the triangular crystals in the rusty area, which is its first discovery among bluish white porcelains. Based on these findings, we discussed the coloring mechanism of iron-spot decoration along with the physical form of the iron oxide crystals, indicating the partially reducing atmosphere during firing process.     

Facile synthesis of Ti3C2 MXene-modified Bi2.15WO6 nanosheets with enhanced reactivity for photocatalytic reduction of Cr(VI)

Through a facile hydrothermal method, we have successfully prepared Ti₃C₂/Bi_2.15WO₆ (TC/BWO) composite, and systematically investigated their reactivity for the photocatalytic reduction of Cr(VI) under visible light. X-ray diffraction and Raman analysis confirm the formation of heterostructure between Bi_2.15WO₆ and Ti₃C₂. The resultant 7TC/BWO composite exhibits enhanced photoactivity toward Cr(VI) reduction. After 120 min irradiation, the conversion of Cr(VI) reaches 92.5% with the quasi-first-order kinetic constant of k = 0.0145 min^?1, which is higher than that of pure BWO (30% and k = 0.0005 min^?1). The electrochemical and photoluminescent characterization confirm that the introduction of Ti₃C₂ is conducive to the separation of carriers, thus significantly improves the photocatalytic performance of TC/BWO. Furthermore, the radical capture experiments verify that the electrons are important for enhancing reduction of Cr(VI) to Cr(III). As a result, this research provides a comprehensive understanding of the reduction of Cr(VI) by TC/BWO composite under visible light.     

Designing independent water transport channels to improve water flooding in ultra-thin nanoporous film cathodes for PEMFCs

Utilization of 3D nanostructured Pt cathodes could obviously improve performances of proton exchange membrane fuel cells (PEMFCs) owing to the reduced tortuosity and the bi-continuous nanoporous structure. However, these cathodes usually suffer from the flooding problem ascribed to the ionomer-free and nanoscale pores which are more susceptible to water condensation. In this paper, ultra-thin nanoporous metal films (100 nm) were utilized to construct PEMFC cathodes and independent transport channels were designed separately for water and gas aiming at the flooding problem. Nanoporous gold (NPG) film was used as the model support for loading Pt nanoparticles owing to its controllable and stable structure. After optimizing the polytetrafluoroethylene (PTFE) content and carbon loading in the gas diffusion layer (GDL), plasma treatment under O₂ atmosphere was used to pattern the GDL with independent water transport channels. The obtained liquid permeation coefficients and oxygen gains demonstrated the obviously improved water and O₂ transport. By using a home-made optimized GDL and a nanoporous film cathode with pore size ～60 nm, the flooding problem could be facilely solved. With a Pt loading of ～16 μg cm^?2, this 3D nanostructured cathode exhibits a PEMFC performance of ～957 mW cm^?2 at 80 °C. The Pt power efficiency is about 4 times higher than that of the commercial Pt/C cathode (50 μg cm^?2, 756 mW cm^?2). Obviously, this study provides a simple but effective methodology to solve the water flooding problem in the ultra-thin nanoporous film cathodes which is applicable for other types of 3D nanostructured PEMFC cathodes.