Using a dual plasma process to produce cobalt--polypyrrole catalysts for the oxygen reduction reaction in fuel cells -- part II: analysing the chemical structure of the films

The chemical structure of cobalt--polypyrrole -- produced by a dual plasma process -- is analysed by means of X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption spectroscopy (NEXAFS), X-ray diffraction (XRD), energy-dispersive X-Ray spectroscopy (EDX) and extended x-ray absorption spectroscopy (EXAFS).It is shown that only nanoparticles of a size of 3\,nm with the low temperature crystal structure of cobalt are present within the compound. Besides that, cobalt--nitrogen and carbon--oxygen structures are observed. Furthermore, more and more cobalt--nitrogen structures are produced when increasing the magnetron power. Linking the information on the chemical structure to the results about the catalytic activity of the films -- which are presented in part I of this contribution -- it is concluded that the cobalt--nitrogen structures are the probable catalytically active sites. The cobalt--nitrogen bond length is calculated as 2.09\,\AA\ and the carbon--nitrogen bond length as 1.38\,\AA

Highly active heterogeneous hydrogenation catalysts prepared from cobalt complexes and rice husk waste

The utilization and valorization of agricultural waste is a key strategy for the implementation of a sustainable economy to lessen the environmental footprint of human activities on Earth. This work describes the use of rice husk (RH) from agricultural waste to prepare a highly active catalyst for the reduction of nitro compounds. RH was impregnated with various cobalt complexes bearing N-donor ligands, then pyrolyzed and the resulting composite was etched with a base to remove the silica domains. The composition and morphology of the prepared materials were investigated by IR, AAS, ICP-OES, XRD, BET, XPS and SEM technics. The material showed excellent activity and selectivity in the hydrogenation of nitro groups in aromatic and aliphatic substrates. A remarkable selectivity towards nitro groups was found in the presence of various reactive functionalities, including halogens, carbonyls, borates, and nitriles. Apart from their excellent activity and selectivity, these catalysts showed remarkable stability, allowing their easy recovery and multiple reuse without requiring re-activation

Different Radial Modification Profiles Observed on APPJ-Treated Polypropylene Surfaces according to the Distance between Plasma Outlet and Target

The plasma jet transfer technique relies on a conductive wire at floating potential, which, upon entering in contact with a primary discharge, is capable of igniting a small plasma plume at the distal end of a long flexible plastic tube. In this work, two different long tube configurations were employed for the surface modification of polypropylene (PP) samples using argon as the working gas. One of the jet configurations has a thin copper (Cu) wire, which was installed inside the long tube. In the other configuration, the floating electrode is a metallic mesh placed between two plastic tubes in a coaxial arrangement. In the first case, the tip of the Cu wire is in direct contact with the working gas at the plasma outlet, whereas, in the second, the inner plastic tube provides an additional dielectric barrier that prevents the conductor from being in contact with the gas. Water contact angle (WCA) measurements on treated PP samples revealed that different surface modification radial profiles are formed when the distance (d) between the plasma outlet and target is changed. Moreover, it was found that the highest WCA reduction does not always occur at the point where the plasma impinges the surface of the material, especially when the d value is small. Through X-ray photoelectron spectroscopy (XPS) analysis, it was confirmed that the WCA values are directly linked to the oxygen-functional groups formed on the PP surfaces after the plasma treatment. An analysis of the WCA measurements along the surface, as well as their temporal evolution, together with the XPS data, suggest that, when the treatment is performed at small d values, the plasma jet removes some functional groups at the point where the plasma hits the surface, thus leading to peculiar WCA profiles

Oxidative Esterification of 5-Hydroxymethylfurfural under Flow Conditions Using a Bimetallic Co/Ru Catalyst

Furanic di-carboxylate derivatives of 5-Hydroxymethylfurfural (HMF) are nowadays important in the polymer industry as they are used as building blocks for bio-based polyesters. The high reactivity of HMF compels to avoid harsh synthetic conditions. Therefore, developing mild catalytic processes for its selective oxidation is a challenging task. Herein, we report the first oxidative esterification of HMF to dimethyl furan-2,5-dicarboxylate (FDCM) under flow conditions using oxygen as oxidant. For that purpose, a new series of nitrogen-doped carbon-supported bimetallic Co/Ru heterogeneous catalysts were prepared and characterized by XRD, XPS and N2 physisorption. These analyses revealed that the porosity of the materials and order of impregnation of the metals to the carbon supports lead to varying catalytic activities. Under optimized conditions the flow reactor showed a 15-fold increase on the production of FDCM compared to batch conditions. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Self-Activation of Inorganic-Organic Hybrids Derived through Continuous Synthesis of Polyoxomolybdate and para-Phenylenediamine Enables Very High Lithium-Ion Storage Capacity

Inorganic-organic hybrid materials with redox-active components were prepared by an aqueous precipitation reaction of ammonium heptamolybdate (AHM) with para-phenylenediamine (PPD). A scalable and low-energy continuous wet chemical synthesis process, known as the microjet process, was used to prepare particles with large surface area in the submicrometer range with high purity and reproducibility on a large scale. Two different crystalline hybrid products were formed depending on the ratio of molybdate to organic ligand and pH. A ratio of para-phenylenediamine to ammonium heptamolybdate from 1 : 1 to 5 : 1 resulted in the compound [C6H10N2]2[Mo8O26] ⋅ 6 H2O, while higher PPD ratios from 9 : 1 to 30 : 1 yielded a composition of [C6H9N2]4[NH4]2[Mo7O24] ⋅ 3 H2O. The electrochemical behavior of the two products was tested in a battery cell environment. Only the second of the two hybrid materials showed an exceptionally high capacity of 1084 mAh g−1 at 100 mA g−1 after 150 cycles. The maximum capacity was reached after an induction phase, which can be explained by a combination of a conversion reaction with lithium to Li2MoO4 and an additional in situ polymerization of PPD. The final hybrid material is a promising material for lithium-ion battery (LIB) applications

X-ray Ptychographic Imaging and Spectroscopic Studies of Plasma-Treated Plastic Films

Polyethylene terephthalate (PET) is a thermoplastic polyester with numerous applications in industry. However, it requires surface modification on an industrial scale for printing and coating processes and plasma treatment is one of the most commonly used techniques to increase the hydrophilicity of the PET films. Systematic improvement of the surface modification by adaption of the plasma process can be aided by a comprehensive understanding of the surface morphology and chemistry. However, imaging large surface areas (tens of microns) with a resolution that allows understanding the surface quality and modification is challenging. As a proof-of-principle, plasma-treated PET films were used to demonstrate the capabilities of X-ray ptychography, currently under development at the soft X-ray free-electron laser FLASH at DESY, for imaging macroscopic samples. In combination with scanning electron microscopy (SEM), this new technique was used to study the effects of different plasma treatment processes on PET plastic films. The studies on the surface morphology were complemented by investigations of the surface chemistry using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). While both imaging techniques consistently showed an increase in roughness and change in morphology of the PET films after plasma treatment, X-ray ptychography can provide additional information on the three-dimensional morphology of the surface. At the same time, the chemical analysis shows an increase in the oxygen content and polarity of the surface without significant damage to the polymer, which is important for printing and coating processes

Making Sense of Complex Carbon and Metal/Carbon Systems by Secondary Electron Hyperspectral Imaging

Carbon and carbon/metal systems with a multitude of functionalities are ubiquitous in new technologies but understanding on the nanoscale remains elusive due to their affinity for interaction with their environment and limitations in available characterization techniques. This paper introduces a spectroscopic technique and demonstrates its capacity to reveal chemical variations of carbon. The effectiveness of this approach is validated experimentally through spatially averaging spectroscopic techniques and using Monte Carlo modeling. Characteristic spectra shapes and peak positions for varying contributions of sp2-like or sp3-like bond types and amorphous hydrogenated carbon are reported under circumstances which might be observed on highly oriented pyrolytic graphite (HOPG) surfaces as a result of air or electron beam exposure. The spectral features identified above are then used to identify the different forms of carbon present within the metallic films deposited from reactive organometallic inks. While spectra for metals is obtained in dedicated surface science instrumentation, the complex relations between carbon and metal species is only revealed by secondary electron (SE) spectroscopy and SE hyperspectral imaging obtained in a state-of-the-art scanning electron microscope (SEM). This work reveals the inhomogeneous incorporation of carbon on the nanoscale but also uncovers a link between local orientation of metallic components and carbon form

Making Sense of Complex Carbon and Metal/Carbon Systems by Secondary Electron Hyperspectral Imaging

Carbon and carbon/metal systems with a multitude of functionalities are ubiquitous in new technologies but understanding on the nanoscale remains elusive due to their affinity for interaction with their environment and limitations in available characterization techniques. This paper introduces a spectroscopic technique and demonstrates its capacity to reveal chemical variations of carbon. The effectiveness of this approach is validated experimentally through spatially averaging spectroscopic techniques and using Monte Carlo modeling. Characteristic spectra shapes and peak positions for varying contributions of sp2-like or sp3-like bond types and amorphous hydrogenated carbon are reported under circumstances which might be observed on highly oriented pyrolytic graphite (HOPG) surfaces as a result of air or electron beam exposure. The spectral features identified above are then used to identify the different forms of carbon present within the metallic films deposited from reactive organometallic inks. While spectra for metals is obtained in dedicated surface science instrumentation, the complex relations between carbon and metal species is only revealed by secondary electron (SE) spectroscopy and SE hyperspectral imaging obtained in a state-of-the-art scanning electron microscope (SEM). This work reveals the inhomogeneous incorporation of carbon on the nanoscale but also uncovers a link between local orientation of metallic components and carbon form