Multi-skeletal PtPdNi nanodendrites as efficient electrocatalyst with high activity and durability towards oxygen reduction reaction

Engineering alloy nanostructures with a combination of highly active noble metals (Pt and Pd) and less electronegative non-noble metal (Ni) is found to be crucial for improving surface reactivity by enriching with active Pt sites. Herein, a multi-skeletal PtPdNi nanodendrites (NDs) was successfully formed by a simple one-pot method with structure directing agent. The modification of Pt electronic structure and their interaction due to compressive strain were explored using benchmark characterization techniques, which showed that the PtPdNi NDs possess Pt-enriched surface, corroborating to more active catalyst sites for oxygen reduction reaction (ORR) in acidic medium. The PtPdNi NDs have a higher electrochemical surface area (63 m² g^?1) and an earlier onset potential (1.01 V) than PtPd NDs, PtNi NDs, and commercial Pt/C catalysts, indicating the outstanding ORR performance. The high mass and specific activities, as well as superior durability after accelerated degradation test (ADT), highlight the remarkable electrocatalytic performance of PtPdNi NDs over others. As a result, enhancing Pt utilization through the formation of PtPdNi NDs could be a reliable strategy to improve ORR electrocatalysis for polymer electrolyte membrane fuel cell (PEMFC) applications.     

Directional separation of hydrogen-containing gas mixture by hydrate-membrane coupling method

Recovery of hydrogen (H₂) from H₂-containing gas mixtures has great significance for energy conservation, cost reduction and benefit increase. However, the common separation methods have the ubiquitous problem due to phase equilibrium principle and results in the conflict between H₂ concentration and H₂ recovery rate in the product gas. Consequently, an innovative conception of hydrate-membrane coupling approach is proposed in this work. In the separation process, hydration and membrane permeation two separation driving forces coexist to achieve the aim of strengthening mass transfer kinetics. H₂ and non-H₂ components (hydrocarbons) are synchronously and directionally selected by membrane and hydrate to improve different phase compositions. Therefore, the gas in feed side could keep relatively high two separation driving forces (H₂ fugacity and hydrocarbons fugacity). The results show that the coupling method could synchronously increase both the concentration and the recovery rate of H₂ in the product gas. At the same time, the volume and concentration of the hydrocarbons in hydrate both increases effectively. It indicates that hydrate and membrane separation methods support each other in the separation process. The hydrate-membrane coupling method fundamentally solves the issue of the decreasing driving force resulting from single separation method and phase equilibrium relationship.     

Numerical simulation of a PEM fuel cell: Effect of tortuosity parameters on the construction of polarization curves

Fuel cells (PEMFCs) are considered a clean alternative for the production of electricity. To improve their efficiency, it is necessary to understand the transport phenomena that determine their performance. This work analyzes the effective diffusion coefficients in the gas diffusion and catalyst layers (GDL and CL, respectively) based on theories such as effective medium approximation and percolation theory of a 3D multiphase nonisothermal model of a single channel PEMFC. We calculate polarization curves with different effective diffusion models and tortuosity factors m, n using OpenFOAM. The best model that approaches to experimental data is the Tomadakis-Sotirchos model with n = 4.0. The exponent m that represents the tortuosity due to the geometry has a high impact on the polarization curve construction compared to the exponent n. High values of diffusibility do not mean high values of current densities showing that there are other phenomena involved, such as water flooding.     

Taylor Bubble Study of the Influence of Fluid Dynamics on Yield and Selectivity in Fast Gas-Liquid Reactions

A consecutive competitive gas-liquid reaction is investigated using a Taylor bubble setup regarding the influence of fluid mixing in the bubble wake on yield and selectivity. The concentration fields behind a Taylor bubble are visualized and measured quantitatively with a novel time-resolved absorption imaging technique based on Beer Lamberts law and an integral selectivity is derived. In addition, the calculation of the local selectivity, often used in numerical approaches, is discussed and the existing experimental limits for its derivation are pointed out. Finally, an increase in selectivity of a competitive consecutive reaction for enhanced mixing is experimentally confirmed.     

A tool for mass transfer evaluation in packed-bed columns for chemical engineering students

This paper presents a Microsoft Excel tool to calculate liquid-gas mass transfer coefficients in packed towers to support numerical design activities in the courses of Unit Operations for Industrial Process and Sustainable Process Design for the Master’s degree in Chemical Engineering of the University of Naples Federico II (Italy).The Mass Transfer Solver Tool (MT Solver Tool) uses several available models to estimate, separately, the values of liquid and gas mass-transfer coefficients and the wet surface area for 144 random and structured packings of interest for absorption/stripping and distillation processes. In addition, a separate spreadsheet can be used in a user-defined mode, to evaluate the mass transfer coefficients with new packing types or to interpret experimental data when the geometrical and physical characteristics of the packing are known. Eventually, the tool is supplied with a data library, where packing geometry and model fitting parameters can be retrieved.The software is aimed to support students and educators in the Unit Operations for Industrial Process and Sustainable Process Design courses. In particular, this is meant to be an example on how the accuracy of design algorithms adopted in unit operation processes is affected by the use of the underpinning correlations for mass transfer rate or pressure drops. Besides, this is aimed to encourage comparison of different correlations when exact field data are not available. Besides, chemical engineers and researchers interested in packed columns design and modelling data may also benefit from the utilization of the software. The MT Solver Tool was introduced to students in a dedicated tutorial lesson after lecturers on packed column design algorithms for distillation, absorption and stripping. Most of the students of the course participated to a group training aimed to simulate the design of an absorption column supported by the MT Solver Tool providing feedback on its application.After the training, an anonymous survey was proposed to the students to monitor the approval rating of the proposed activity and the use of the MT Solver Tool software to support numerical calculations.     

Influence of the Impaction Angle on the Triboelectric Charging of Aerosol Nanoparticles

A low pressure impactor is used to measure triboelectric charging behavior of metallic nanoparticles. Ag nanoparticles, produced by spark discharge, were impacted onto Pt sputtered targets. The influence of the impaction angle and impaction velocity on the triboelectric charging was investigated. While for perpendicular impaction the charge transfer behavior of previous work was confirmed, the oblique impaction revealed new phenomena. Additional charge transfer was observable, which increases with obliqueness. The possibility of mass transfer between particle and target due to the high-energy collisions was also investigated. SEM characterization and Auger spectroscopy indicate mass transfer from the particle to the target surface.     

The control of paracetamol particle size and surface morphology through crystallisation in a spray dryer

The parameters governing the crystallisation of paracetamol using various conventional techniques has been extensively studied, however the factors influencing the drug crystallisation using spray drying is not as well understood. The aim of this work was to investigate the crystallisation of an active pharmaceutical ingredient through evaporative crystallisation using a spray dryer to study the physicochemical properties of the drug and to use semi-empirical equations to gain insight into the morphology and particle size of the dried powder. Paracetamol solutions were spray dried at various inlet temperatures ranging from 60 °C to 120 °C and also from a series of inlet feed solvent compositions ranging from 50/50% v/v ethanol/water to 100% ethanol and solid-state characterisation was done. The size and morphology of the dried materials were altered with a change in spray drying parameters, with an increase in inlet temperature leading to an increase in particle Sauter mean diameter (from 3.0 to 4.4 µm) and a decrease in the particle size with an increase in ethanol concentration in the feed (from 4.6 to 4.4 µm) as a result of changes in particle density and atomised droplet size. The morphology of the dried particles consisted of agglomerates of individual crystallites bound together into larger semi-spherical agglomerates with a higher tendency for particles having crystalline ridges to form at higher ethanol concentrations of the feed.     

Enhanced graphitic domains of unreduced graphene oxide and the interplay of hydration behaviour and catalytic activity

Previous studies indicate that the properties of graphene oxide (GO) can be significantly improved by enhancing its graphitic domain size through thermal diffusion and clustering of functional groups. Remarkably, this transition takes place below the decomposition temperature of the functional groups and thus allows fine tuning of graphitic domains without compromising with the functionality of GO. By studying the transformation of GO under mild thermal treatment, we directly observe this size enhancement of graphitic domains from originally ≤40 nm² to >200 nm² through an extensive transmission electron microscopy (TEM) study. Additionally, we confirm the integrity of the functional groups during this process by a comprehensive chemical analysis. A closer look into the process confirms the theoretical predicted relevance for the room temperature stability of GO and the development of the composition of functional groups is explained with reaction pathways from theoretical calculations. We further investigate the influence of enlarged graphitic domains on the hydration behaviour of GO and the catalytic performance of single atom catalysts supported by GO. Additionally, we show that the sheet resistance of GO is reduced by several orders of magnitude during the mild thermal annealing process.