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N-doped carbon (N-C) materials are increasingly popular in different electrochemical and catalytic applications. Due to the structural and stoichiometric diversity of these materials, however, the role of different functional moieties is still controversial. We have synthesized a set of N-C catalysts, with identical morphologies (∼27 nm pore size). By systematically changing the precursors, we have varied the amount and chemical nature of N-functions on the catalyst surface. The CO2 reduction (CO2R) properties of these catalysts were tested in both electrochemical (EC) and thermal catalytic (TC) experiments (i.e., CO2 + H2 reaction). CO was the major CO2R product in all cases, while CH4 appeared as a minor product. Importantly, the CO2R activity changed with the chemical composition, and the activity trend was similar in the EC and TC scenarios. The activity was correlated with the amount of different N-functions, and a correlation was found for the -NO x species. Interestingly, the amount of this species decreased radically during EC CO2R, which was coupled with the performance decrease. The observations were rationalized by the adsorption/desorption properties of the samples, while theoretical insights indicated a similarity between the EC and TC paths.

Different Co contents were used to tune bimetallic Pt–Co nanoparticles with a diameter of 8 nm, resulting in Pt:Co ratios of 3.54, 1.51, and 0.96. These nanoparticles were then applied to the MCF-17 mesoporous silica support. The synthesized materials were characterized with HR-TEM, HAADF-TEM, EDX, XRD, BET, ICP-MS, in situ DRIFTS, and quasi in situ XPS techniques. The catalysts were tested in a thermally induced reverse water–gas shift reaction (CO2:H2 = 1:4) at atmospheric pressure in the 200–700 °C temperature range. All bimetallic Pt–Co particles outperformed the pure Pt benchmark catalyst. The nanoparticles with a Pt:Co ratio of 1.51 exhibited 2.6 times higher activity and increased CO selectivity by 4% at 500 °C. Experiments proved that the electron accumulation and alloying effect on the Pt–Co particles are stronger with higher Co ratios. The production of CO followed the formate reaction pathway on all catalysts due to the face-centered-cubic structure, which is similar to the Pt benchmark. It is concluded that the enhanced properties of Co culminate at a Pt:Co ratio of 1.51 because decreasing the ratio to 0.96 results in lower activity despite having more Co atoms available for the electronic interaction, resulting in the lack of electron-rich Pt sites. [ABSTRACT FROM AUTHOR]

The implementation of supported metal catalysts heavily relies on the synergistic interactions between metal nanoparticles and the material they are dispersed on. It is clear that interfacial perimeter sites have outstanding skills for turning catalytic reactions over, however, high activity and selectivity of the designed interface‐induced metal distortion can also obtain catalysts for the most crucial industrial processes as evidenced in this paper. Herein, the beneficial synergy established between designed Pt nanoparticles and MnO in the course of the reverse water gas shift (RWGS) reaction resulted in a Pt/MnO catalyst having ≈10 times higher activity compared to the reference Pt/SBA‐15 catalyst with >99 % CO selectivity. Under activation, a crystal assembly through the metallic Pt (110) and MnO evolved, where the plane distance differences caused a mismatched‐row structure in softer Pt nanoparticles, which was identified by microscopic and surface‐sensitive spectroscopic characterizations combined with density functional theory simulations. The generated edge dislocations caused the Pt lattice expansion which led to the weakening of the Pt−CO bond. Even though MnO also exhibited an adverse effect on Pt by lowering the number of exposed metal sites, rapid desorption of the linearly adsorbed CO species governed the performance of the Pt/MnO in the RWGS. [ABSTRACT FROM AUTHOR]

Highly porous metal oxide–polymer nanocomposites are attracting considerable interest due to their unique structural and functional features. A porous polymer matrix brings properties such as high porosity and permeability, while the metal oxide phase adds functionality. For the metal oxide phase to perform its function, it must be fully accessible, and this is possible only at the pore surface, but functioning surfaces require controlled engineering, which remains a challenge. Here, highly porous nanocomposite beads based on thin metal oxide nanocoatings and polymerized high internal phase emulsions (polyHIPEs) are demonstrated. By leveraging the unique properties of polyHIPEs, i.e., a three-dimensional (3D) interconnected network of macropores, and high-precision of the atomic-layer-deposition technique (ALD), we were able to homogeneously coat the entire surface of the pores in polyHIPE beads with TiO2-, ZnO-, and Al2O3-based nanocoatings. Parameters such as nanocoating thickness, growth per cycle (GPC), and metal oxide (MO) composition were systematically controlled by varying the number of deposition cycles and dosing time under specific process conditions. The combination of polyHIPE structure and ALD technique proved advantageous, as MO-nanocoatings with thicknesses between 11 ± 3 and 40 ± 9 nm for TiO2 or 31 ± 6 and 74 ± 28 nm for ZnO and Al2O3, respectively, were successfully fabricated. It has been shown that the number of ALD cycles affects both the thickness and crystallinity of the MO nanocoatings. Finally, the potential of ALD-derived TiO2-polyHIPE beads in photocatalytic oxidation of an aqueous bisphenol A (BPA) solution was demonstrated. The beads exhibited about five times higher activity than nanocomposite beads prepared by the conventional (Pickering) method. Such ALD-derived polyHIPE nanocomposites could find wide application in nanotechnology, sensor development, or catalysis. [ABSTRACT FROM AUTHOR]

A low ratio of polymerization is a major problem in resin-based composites. In this paper, the plasmonic effect of gold-covered silica nanoparticles on the physicochemical and mechanical properties of bisphenol A diglycidyl dimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA) green light-photopolymerizable dental resin was investigated at an intensity of 1.4 mW/cm2 for 40 s. Transmission electron microscopy (TEM) showed silica of about 350 nm covered with 12–15 nm gold nanoparticles (Au NPs) at 100% nominal coverage. Five different concentrations of bare and patchy silica particles were used; in the latter composite, the calculated Au wt% were 0.0052 wt%, 0.0104 wt%, 0.0208 wt%, 0.04160 wt%, and 0.0823 wt%. The plasmon peak of patchy silica-filled nanocomposite overlapped with the absorption of Irgacure 784 photoinitiator and green LED light emission peak. The effect of plasmon-enhanced polymerization achieved with green light illumination was analyzed using diametral tensile strength (DTS), differential scanning calorimetry (DSC), surface plasmon resonance imaging (SPRi), and degree of conversion (DC) based on Raman spectroscopy. The values of the Au NP with 0.0208 wt% was found to be maximum in all the measured data. Based on our result, it can be concluded that the application of patchy silica particles in dental resin can improve the polymerization ratio and the mechanical parameters of the composite. [ABSTRACT FROM AUTHOR]

High‐resolution computed tomography (micro‐CT) was used in this paper to visualize the inner structure of lithium nickel cobalt aluminum oxide 18 650 form‐factor batteries non‐destructively after and during a heat endurance test. Open circuit relaxation and electrochemical impedance spectroscopy were also conducted. We tested the different heat‐aged cells with micro‐CT and charge‐discharge and electrochemical impedance spectroscopy measurements to find the observable physical changes in the cell and connect them to the loss of performance. We found that the drastic changes in the structure of the cell at higher temperatures are well traceable. At 150 °C layer delamination and performance loss were observed, battery failure occurred with the further increase of the temperature, while at the same time, precipitation appeared and the positive temperature coefficient device fractured. Without opening the cell only tomographic methods can provide insight into the inner structure of the cell. We were able to measure the changes in the distances of the layers of the battery and decent shrinkage was observed, which can be linked to the loss of capacity and increased resistance. [ABSTRACT FROM AUTHOR]

Glucose-to-fructose isomerization is the key process in the reaction sequence that can lead to the total conversion of biomass into valuable fine chemicals. However, it is challenging to find an efficient, cost-effective- and waste-minimized process to produce High Fructose Corn Syrup (HFCS) without using non-green approaches. To this end, hydrotalcite (MgAl-layered double hydroxides (MgAl-LDH)) catalyzed glucose isomerization in ethanol seemed to be one of the most promising processes in the last decade. In contrast to the well-studied reaction carried out in aqueous solutions, when ethanolic solutions are used, many potentially important properties of the LDHs cannot be studied in terms of how they affect their own catalytic abilities. Neither the effect of the basic site distribution, nor the morphological aspects and the role of surface hydration have been elucidated so far. In this study, the systematic alteration of the textural and structural parameters of hydrotalcites and hydrocalumites (Ca2Al-LDH) revealed clear structure–activity-selectivity relationships. These indicate that the rate-determining factor is the hydrophilicity and the LDH surface factors affecting it, which determine the catalytic performance of the LDH catalyst more than any other factor. This is evidenced by the fact that the catalytic efficiency of hydrotalcites can be improved by reducing their basicity. When isomerizations catalyzed by the easily recyclable LDH with suitable surface features are carried out, a truly similar catalytic performance (71% glucose conversion, 83% fructose selectivity, 59% fructose yield) can be achieved as was previously described, but at a significantly lower reaction temperature (120 °C → 80 °C). [ABSTRACT FROM AUTHOR]

A quick overview of the increasing pollutants worldwide shows a parallel movement toward strict legalization to limit contamination of air before it gets out of hand, however, in this paper, we are discussing a source of emissions that is yet to receive its' deserved attention rendered in non-road mobile machinery. Our proposal to solve this issue unfolds by delivering an efficient catalyst, starting by characterizing its relevant properties such as the choice of material, the shape of the catalyst, the chemical structure, and the active coating agent. So, in this sequence of experiments, we are investigating the performance of five ceramic supports impregnated with 0.1 and 0.2 wt% palladium (II). Starting by testing the samples' ability to oxidize CO in a fixed bed reactor, we will measure their performance in converting flue-gas emissions by testing the samples on a custom-designed catalytic converter connected to a dynamometer system. Following this study, we can achieve an outstanding 98% reduction in NOx and 95% reduction in CO and build a direct relation between sample properties and performance. For now, this research will be the first part of a tailored proposed solution to reduce NRMM emissions using a catalytic converter where this paper will mostly be concerned with the overall performance of the catalyst. [ABSTRACT FROM AUTHOR]

Strontium titanate (STO) photocatalysts were prepared via a slightly modified Pechini sol–gel method. A unique rapid calcination technique with a short exposure time was used to obtain crystalline products. The samples were characterized by X-ray diffractometry, scanning electron microscopy, diffuse reflectance spectroscopy, infrared spectroscopy, nitrogen adsorption–desorption measurements, and X-ray photoelectron spectroscopy. Their photocatalytic activity was evaluated by the photocatalytic oxidation of phenol, oxalic acid, and chlorophenol under UV light irradiation using commercial STO as a reference. These pollutants, together with glucose and propanol, were used to investigate the stability of the samples against various functional groups. All our samples exhibited higher photocatalytic activity than the commercial STO reference. With increasing calcination temperature, the crystallinity and primary crystallite sizes increased while the band gaps and specific surface areas decreased. The photocatalytic activity of the most efficient sample was explained by the presence of SrCO3 on its surface. The STO catalysts were highly stable as they largely retained their crystalline composition after exposure to chemicals with different functional groups. Finally, we compared the costs associated with the unique calcination technique with a more conventional one and found that our method is ~35% more cost-effective. [ABSTRACT FROM AUTHOR]

The steam reforming of ethanol (SRE) is a key process for the production of H2 and other vital hydrocarbons. The present work describes the synthesis of Platinum‐Gallium (Pt−Ga) nanoalloys supported on mesostructured cellular foam (MCF‐17) via ultrasound‐assisted impregnation method. Ga was substituted with Pt in different wt.% i. e. Pt/MCF‐17, Pt99.9Ga0.1/MCF‐17, Pt99Ga1/MCF‐17, and Pt90Ga10/MCF‐17 and was evaluated towards the SRE at a temperature range of 473K‐773 K towards hydrogen (H2), acetaldehyde (CH3CHO), diethylether (DEE), ethylene (C2H4), carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and ethane (C2H6). The SRE activity and H2 formation rate with Pt90Ga10/MCF‐17 catalyst were observed to be 68.1 % and 3047.2 nmole g−1 sec−1, which is 9.8 and 4.5 times more than the Pt/MCF‐17 counterparts. Moreover, as observed from DRIFTS, NH3‐TPD and XPS studies Ga showed high interaction with Pt in the electron deficit state which resulted in the increased dehydrogenating and acidic properties that resulted in a higher yield of H2. [ABSTRACT FROM AUTHOR]