“Flowing Atmospheric Pressure Afterglow for Ambient Ionization: Reaction Pathways Revealed by Modeling”. Aghaei M, Bogaerts A, Analytical Chemistry 93, 6620 (2021). http://doi.org/10.1021/acs.analchem.0c04076
Abstract: We describe the plasma chemistry in a helium flowing atmospheric pressure afterglow (FAPA) used for analytical spectrometry, by means of a quasione-dimensional (1D) plasma chemical kinetics model. We study the effect of typical impurities present in the feed gas, as well as the afterglow in ambient humid air. The model provides the species density profiles in the discharge and afterglow regions and the chemical pathways. We demonstrate that H, N, and O atoms are formed in the discharge region, while the dominant reactive neutral species in the afterglow are O3 and NO. He* and He2* are responsible for Penning ionization of O2, N2, H2O, H2, and N, and especially O and H atoms. Besides, He2+ also contributes to ionization of N2, O2, H2O, and O through charge transfer reactions. From the pool of ions created in the discharge, NO+ and (H2O)3H+ are the dominant ions in the afterglow. Moreover, negatively charged clusters, such as NO3H2O− and NO2H2O−, are formed and their pathway is discussed as well. Our model predictions are in line with earlier observations in the literature about the important reagent ions and provide a comprehensive overview of the underlying pathways. The model explains in detail why helium provides a high analytical sensitivity because of high reagent ion formation by both Penning ionization and charge transfer. Such insights are very valuable for improving the analytical performance of this (and other) ambient desorption/ionization source(s).
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 6.32
DOI: 10.1021/acs.analchem.0c04076
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“Distribution of fields and charge carriers in cylindrical nanosize silicon-based metal-oxide-semiconductor structures”. Pokatilov EP, Fomin VM, Balaban SN, Gladilin VN, Klimin SN, Devreese JT, Magnus W, Schoenmaker W, Collaert N, van Rossum M, de Meyer K, Journal Of Applied Physics 85, 6625 (1999). http://doi.org/10.1063/1.370171
Keywords: A1 Journal article; Electron Microscopy for Materials Science (EMAT);
Impact Factor: 2.068
Times cited: 16
DOI: 10.1063/1.370171
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“Long-Range Domain Structure and Symmetry Engineering by Interfacial Oxygen Octahedral Coupling at Heterostructure Interface”. Liao Z, Green RJ, Gauquelin N, Macke S, Li L, Gonnissen J, Sutarto R, Houwman EP, Zhong Z, Van Aert S, Verbeeck J, Sawatzky GA, Huijben M, Koster G, Rijnders G, Advanced functional materials 26, 6627 (2016). http://doi.org/10.1002/adfm.201602155
Abstract: In epitaxial thin film systems, the crystal structure and its symmetry deviate from the bulk counterpart due to various mechanisms such as epitaxial strain and interfacial structural coupling, which is accompanyed by a change in their properties. In perovskite materials, the crystal symmetry can be described by rotations of sixfold coordinated transition metal oxygen octahedra, which are found to be altered at interfaces. Here, it is unraveled how the local oxygen octahedral coupling at perovskite heterostructural interfaces strongly influences the domain structure and symmetry of the epitaxial films resulting in design rules to induce various structures in thin films using carefully selected combinations of substrate/buffer/film. Very interestingly it is discovered that these combinations lead to structure changes throughout the full thickness of the film. The results provide a deep insight into understanding the origin of induced structures in a perovskite heterostructure and an intelligent route to achieve unique functional properties.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 12.124
Times cited: 23
DOI: 10.1002/adfm.201602155
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“S-SIMS and MetA-SIMS study of organic additives in thin polymer coatings”. Adriaensen L, Vangaever F, Lenaerts J, Gijbels R, Applied surface science 252, 6628 (2006). http://doi.org/10.1016/j.apsusc.2006.02.275
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 3.387
Times cited: 3
DOI: 10.1016/j.apsusc.2006.02.275
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“Quantitative Tomography of Organic Photovoltaic Blends at the Nanoscale”. Pfannmöller M, Heidari H, Nanson L, Lozman OR, Chrapa M, Offermans T, Nisato G, Bals S, Nano letters 15, 6634 (2015). http://doi.org/10.1021/acs.nanolett.5b02437
Abstract: The success of semiconducting organic materials has enabled green technologies for electronics, lighting, and photovoltaics. However, when blended together, these materials have also raised novel fundamental questions with respect to electronic, optical, and thermodynamic properties. This is particularly important for organic photovoltaic cells based on the bulk heterojunction. Here, the distribution of nanoscale domains plays a crucial role depending on the specific device structure. Hence, correlation of the aforementioned properties requires 3D nanoscale imaging of materials domains, which are embedded in a multilayer device. Such visualization has so far been elusive due to lack of contrast, insufficient signal, or resolution limits. In this Letter, we introduce spectral scanning transmission electron tomography for reconstruction of entire volume plasmon spectra from rod-shaped specimens. We provide 3D structural correlations and compositional mapping at a resolution of approximately 7 nm within advanced organic photovoltaic tandem cells. Novel insights that are obtained from quantitative 3D analyses reveal that efficiency loss upon thermal annealing can be attributed to subtle, fundamental blend properties. These results are invaluable in guiding the design and optimization of future devices in plastic electronics applications and provide an empirical basis for modeling and simulation of organic solar cells.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 12.712
Times cited: 26
DOI: 10.1021/acs.nanolett.5b02437
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“Selective laser-assisted synthesis of tubular van der Waals heterostructures of single-layered PbI2 within carbon nanotubes exhibiting carrier photogeneration”. Sandoval S, Kepic D, Perez del Pino A, Gyorgy E, Gomez A, Pfannmöller M, Van Tendeloo G, Ballesteros B, Tobias G, ACS nano 12, 6648 (2018). http://doi.org/10.1021/ACSNANO.8B01638
Abstract: The electronic and optical properties of two-dimensional layered materials allow the miniaturization of nanoelectronic and optoelectronic devices in a competitive manner. Even larger opportunities arise when two or more layers of different materials are combined. Here, we report on an ultrafast energy efficient strategy, using laser irradiation, which allows bulk synthesis of crystalline single-layered lead iodide in the cavities of carbon nanotubes by forming cylindrical van der Waals heterostructures. In contrast to the filling of van der Waals solids into carbon nanotubes by conventional thermal annealing, which favors the formation of inorganic nanowires, the present strategy is highly selective toward the growth of monolayers forming lead iodide nanotubes. The irradiated bulk material bearing the nanotubes reveals a decrease of the resistivity as well as a significant increase in the current flow upon illumination. Both effects are attributed to the presence of single-walled lead iodide nanotubes in the cavities of carbon nanotubes, which dominate the properties of the whole matrix. The present study brings in a simple, ultrafast and energy efficient strategy for the tailored synthesis of rolled-up single-layers of lead iodide (i.e., single-walled PbI2 nanotubes), which we believe could be expanded to other two-dimensional (2D) van der Waals solids. In fact, initial tests with ZnI2 already reveal the formation of single-walled ZnI2 nanotubes, thus proving the versatility of the approach.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 13.942
Times cited: 8
DOI: 10.1021/ACSNANO.8B01638
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“Empirical evaluation of metal deposition for the analysis of organic compounds with static secondary ion mass spectrometry (S-SIMS)”. de Mondt R, Adriaensen L, Vangaever F, Lenaerts J, van Vaeck L, Gijbels R, Applied surface science 252, 6652 (2006). http://doi.org/10.1016/j.apsusc.2006.02.110
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 3.387
Times cited: 9
DOI: 10.1016/j.apsusc.2006.02.110
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“Atomistic modelling of CVD synthesis of carbon nanotubes and graphene”. Elliott JA, Shibuta Y, Amara H, Bichara C, Neyts EC, Nanoscale 5, 6662 (2013). http://doi.org/10.1039/c3nr01925j
Abstract: We discuss the synthesis of carbon nanotubes (CNTs) and graphene by catalytic chemical vapour deposition (CCVD) and plasma-enhanced CVD (PECVD), summarising the state-of-the-art understanding of mechanisms controlling their growth rate, chiral angle, number of layers (walls), diameter, length and quality (defects), before presenting a new model for 2D nucleation of a graphene sheet from amorphous carbon on a nickel surface. Although many groups have modelled this process using a variety of techniques, we ask whether there are any complementary ideas emerging from the different proposed growth mechanisms, and whether different modelling techniques can give the same answers for a given mechanism. Subsequently, by comparing the results of tight-binding, semi-empirical molecular orbital theory and reactive bond order force field calculations, we demonstrate that graphene on crystalline Ni(111) is thermodynamically stable with respect to the corresponding amorphous metal and carbon structures. Finally, we show in principle how a complementary heterogeneous nucleation step may play a key role in the transformation from amorphous carbon to graphene on the metal surface. We conclude that achieving the conditions under which this complementary crystallisation process can occur may be a promising method to gain better control over the growth processes of both graphene from flat metal surfaces and CNTs from catalyst nanoparticles.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 7.367
Times cited: 52
DOI: 10.1039/c3nr01925j
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“Catalyzed growth of carbon nanotube with definable chirality by hybrid molecular dynamics-force biased Monte Carlo simulations”. Neyts EC, Shibuta Y, van Duin ACT, Bogaerts A, ACS nano 4, 6665 (2010). http://doi.org/10.1021/nn102095y
Abstract: Metal-catalyzed growth mechanisms of carbon nanotubes (CNTs) were studied by hybrid molecular dynamics−Monte Carlo simulations using a recently developed ReaxFF reactive force field. Using this novel approach, including relaxation effects, a CNT with definable chirality is obtained, and a step-by-step atomistic description of the nucleation process is presented. Both root and tip growth mechanisms are observed. The importance of the relaxation of the network is highlighted by the observed healing of defects.
Keywords: A1 Journal article; Engineering sciences. Technology; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 13.942
Times cited: 129
DOI: 10.1021/nn102095y
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“Synthesis and Characterization of Double Solid Solution (Zr,Ti)(2)(Al,Sn)C MAX Phase Ceramics”. Tunca B, Lapauw T, Delville R, Neuville DR, Hennet L, Thiaudiere D, Ouisse T, Hadermann J, Vleugels J, Lambrinou K, Inorganic chemistry 58, 6669 (2019). http://doi.org/10.1021/ACS.INORGCHEM.9B00065
Abstract: Quasi phase-pure (>98 wt %) MAX phase solid solution ceramics with the (ZryTi)(2)(Al-0.5,Sn-0.5)C stoichiometry and variable Zr/Ti ratios were synthesized by both reactive hot pressing and pressureless sintering of ZrH2, TiH2, Al, Sn, and C powder mixtures. The influence of the different processing parameters, such as applied pressure and sintering atmosphere, on phase purity and microstructure of the produced ceramics was investigated. The addition of Sn to the (Zr,Ti)(2)AlC system was the key to achieve phase purity. Its effect on the crystal structure of a 211-type MAX phase was assessed by calculating the distortions of the octahedral M6C and trigonal M(6)A prisms due to steric effects. The M(6)A prismatic distortion values were found to be smaller in Sn-containing double solid solutions than in the (Zr,Ti)(2)AlC MAX phases. The coefficients of thermal expansion along the < a > and < c > directions were measured by means of Rietveld refinement of high-temperature synchrotron X-ray diffraction data of (Zr1-x,Ti-x)(2)(Al-0.5,Sn-0.5)C MAX phase solid solutions with x = 0, 0.3, 0.7, and 1. The thermal expansion coefficient data of the Ti-2(Al-0.5,Sn-0.5)C solid solution were compared with those of the Ti2AlC and Ti2SnC ternary compounds. The thermal expansion anisotropy increased in the (Zr,Ti)(2)(Al-0.5,Sn-0.5)C double solid solution MAX phases as compared to the Zr-2(Al-0.5,Sn-0.5)C and Ti-2(Al-0.5,Sn-0.5)C end-members.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 3
DOI: 10.1021/ACS.INORGCHEM.9B00065
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“Observation of surface species in plasma-catalytic dry reforming of methane in a novel atmospheric pressure dielectric barrier discharge in situ IR cell”. Van Turnhout J, Aceto D, Travert A, Bazin P, Thibault-Starzyk F, Bogaerts A, Azzolina-Jury F, Catalysis Science &, Technology 12, 6676 (2022). http://doi.org/10.1039/D2CY00311B
Abstract: We developed a novel in situ (i.e. inside plasma and during operation) IR dielectric barrier discharge cell allowing investigation of plasma catalysis in transmission mode, atmospheric pressure, flow conditions (WHSV similar to 0-50 000 mL g(-1) h(-1)), at relevant discharge voltages (similar to 0-50 kV) and frequencies (similar to 0-5 kHz). We applied it to study the IR-active surface species formed on a SiO2 support and on a 3 wt% Ru/SiO2 catalyst, which can help to reveal the important surface reaction mechanisms during the plasma-catalytic dry reforming of methane (DRM). Moreover, we present a technique for the challenging task of estimating the temperature of a catalyst sample in a plasma-catalytic system in situ and during plasma operation. We found that during the reaction, water is immediately formed at the SiO2 surface, and physisorbed formic acid is formed with a delay. As Ru/SiO2 is subject to greater plasma-induced heating than SiO2 (with a surface temperature increase in the range of 70-120 degrees C, with peaks up to 150 degrees C), we observe lower amounts of physisorbed water on Ru/SiO2, and less physisorbed formic acid formation. Importantly, the formation of surface species on the catalyst sample in our plasma-catalytic setup, as well as the observed conversions and selectivities in plasma conditions, can not be explained by plasma-induced heating of the catalyst surface, but must be attributed to other plasma effects, such as the adsorption of plasma-generated radicals and molecules, or the occurrence of Eley-Rideal reactions.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 5
DOI: 10.1039/D2CY00311B
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“3D characterization of the structural transformation undergone by Cu@Ag core-shell nanoparticles following CO₂, reduction reaction”. Arenas Esteban D, Pacquets L, Choukroun D, Hoekx S, Kadu AA, Schalck J, Daems N, Breugelmans T, Bals S, Chemistry of materials 35, 6682 (2023). http://doi.org/10.1021/ACS.CHEMMATER.3C00649
Abstract: The increasing use of metallic nanoparticles (NPs) is significantly advancing the field of electrocatalysis. In particular, Cu/Ag bimetallic interfaces are widely used to enhance the electrochemical CO2 reduction reaction (eCO(2)RR) toward CO and, more recently, C-2 products. However, drastic changes in the product distribution and performance when Cu@Ag core-shell configurations are used can often be observed under electrochemical reaction conditions, especially during the first few minutes of the reaction. Possible structural changes that generate these observations remain underexplored; therefore, the structure-property relationship is hardly understood. In this study, we use electron tomography to investigate the structural transformation mechanism of Cu@Ag core-shells NPs during the critical first minutes of the eCO(2)RR. In this manner, we found that the crystallinity of the Cu seed determines whether the formation of a complete and homogeneous Ag shell is possible. Moreover, by tracking the particles' transformations, we conclude that modifications of the Cu-Ag interface and Cu2O enrichment at the surface of the NPs are key factors contributing to the product generation changes. These insights provide a better understanding of how bimetallic core-shell NPs transform under electrochemical conditions.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT); Applied Electrochemistry & Catalysis (ELCAT)
Impact Factor: 8.6
Times cited: 1
DOI: 10.1021/ACS.CHEMMATER.3C00649
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“Gas phase deposition of well-defined bimetallic gold-silver clusters for photocatalytic applications”. Chinnabathini VC, Dingenen F, Borah R, Abbas I, van der Tol J, Zarkua Z, D'Acapito F, Nguyen THT, Lievens P, Grandjean D, Verbruggen SW, Janssens E, Nanoscale 15, 6696 (2023). http://doi.org/10.1039/D2NR07287D
Abstract: Cluster beam deposition is employed for fabricating well-defined bimetallic plasmonic photocatalysts to enhance their activity while facilitating a more fundamental understanding of their properties. AuxAg1-x clusters with compositions (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) spanning the metals' miscibility range were produced in the gas-phase and soft-landed on TiO2 P25-coated silicon wafers with an optimal coverage of 4 atomic monolayer equivalents. Electron microscopy images show that at this coverage most clusters remain well dispersed whereas EXAFS data are in agreement with the finding that the deposited clusters have an average size of ca. 5 nm and feature the same composition as the ablated alloy targets. A composition-dependant electron transfer from Au to Ag that is likely to impart chemical stability to the bimetallic clusters and protect Ag atoms against oxidation is additionally evidenced by XPS and XANES. Under simulated solar light, AuxAg1-x clusters show a remarkable composition-dependent volcano-type enhancement of their photocatalytic activity towards degradation of stearic acid, a model compound for organic fouling on surfaces. The Formal Quantum Efficiency (FQE) is peaking at the Au0.3Ag0.7 composition with a value that is twice as high as that of the pristine TiO2 P25 under solar simulator. Under UV the FQE of all compositions remains similar to that of pristine TiO2. A classical electromagnetic simulation study confirms that among all compositions Au0.3Ag0.7 features the largest near-field enhancement in the wavelength range of maximal solar light intensity, as well as sufficient individual photon energy resulting in a better photocatalytic self-cleaning activity. This allows ascribing the mechanism for photocatalysis mostly to the plasmonic effect of the bimetallic clusters through direct electron injection and near-field enhancement from the resonant cluster towards the conduction band of TiO2. These results not only demonstrate the added value of using well-defined bimetallic nanocatalysts to enhance their photocatalytic activity but also highlights the potential of the cluster beam deposition to design tailored noble metal modified photocatalytic surfaces with controlled compositions and sizes without involving potentially hazardous chemical agents.
Keywords: A1 Journal article; Engineering sciences. Technology
Impact Factor: 6.7
DOI: 10.1039/D2NR07287D
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“Crystallographic shear structures as a route to anion-deficient perovskites”. Abakumov AM, Hadermann J, Bals S, Nikolaev IV, Antipov EV, Van Tendeloo G, Angewandte Chemie: international edition in English 45, 6697 (2006). http://doi.org/10.1002/anie.200602480
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 11.994
Times cited: 62
DOI: 10.1002/anie.200602480
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“Shape Control of Colloidal Cu2-x S Polyhedral Nanocrystals by Tuning the Nucleation Rates”. van der Stam W, Gradmann S, Altantzis T, Ke X, Baldus M, Bals S, de Mello Donega C, Chemistry of materials 28, 6705 (2016). http://doi.org/10.1021/acs.chemmater.6b03098
Abstract: Synthesis protocols for colloidal nanocrystals (NCs) with narrow size and shape distributions are of particular interest for the successful implementation of these nanocrystals into devices. Moreover, the preparation of NCs with well-defined crystal phases is of key importance. In this work, we show that Sn(IV)-thiolate complexes formed in situ strongly influence the nucleation and growth rates of colloidal Cu2-x S polyhedral NCs, thereby dictating their final size, shape, and crystal structure. This allowed us to successfully synthesize hexagonal bifrustums and hexagonal bipyramid NCs with low-chalcocite crystal structure, and hexagonal nanoplatelets with various thicknesses and aspect ratios with the djurleite crystal structure, by solely varying the concentration of Sn(IV)-additives (namely, SnBr4) in the reaction medium. Solution and solid-state 119Sn NMR measurements show that SnBr4 is converted in situ to Sn(IV)-thiolate complexes, which increase the Cu2-x S nucleation barrier without affecting the precursor conversion rates. This influences both the nucleation and growth rates in a concentration-dependent fashion and leads to a better separation between nucleation and growth. Our approach of tuning the nucleation and growth rates with in situ-generated Sn-thiolate complexes might have a more general impact due to the availability of various metal-thiolate complexes, possibly resulting in polyhedral NCs of a wide variety of metal-sulfide compositions.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 27
DOI: 10.1021/acs.chemmater.6b03098
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“Plasma-Catalytic Ammonia Synthesis beyond the Equilibrium Limit”. Mehta P, Barboun PM, Engelmann Y, Go DB, Bogaerts A, Schneider WF, Hicks JC, Acs Catalysis 10, 6726 (2020). http://doi.org/10.1021/acscatal.0c00684
Abstract: We explore the consequences of nonthermal plasma-activation on product yields in catalytic ammonia synthesis, a reaction that is equilibrium-limited at elevated temperatures. We employ a minimal microkinetic model that incorporates the influence of plasma-activation on N2 dissociation rates to predict NH3 yields into and across the equilibrium-limited regime. NH3 yields are predicted to exceed bulk thermodynamic equilibrium limits on materials that are thermal-rate-limited by N2 dissociation. In all cases, yields revert to bulk equilibrium at temperatures at which thermal reaction rates exceed plasma-activated ones. Beyond-equilibrium NH3 yields are observed in a packed bed dielectric barrier discharge reactor and exhibit sensitivity to catalytic material choice in a way consistent with model predictions. The approach and results highlight the opportunity to exploit synergies between nonthermal plasmas and catalysts to affect transformations at conditions inaccessible through thermal routes.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 12.9
DOI: 10.1021/acscatal.0c00684
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“Capture-ferment-upgrade : a three-step approach for the valorization of sewage organics as commodities”. Alloul A, Ganigue R, Spiller M, Meerburg F, Cagnetta C, Rabaey K, Vlaeminck SE, Environmental science and technology 52, 6729 (2018). http://doi.org/10.1021/ACS.EST.7B05712
Abstract: This critical review outlines a roadmap for the conversion of chemical oxygen demand (COD) contained in sewage to commodities based on three-steps: capture COD as sludge, ferment it to volatile fatty acids (VFA), and upgrade VFA to products. The article analyzes the state-of-the-art of this three step approach and discusses the bottlenecks and challenges. The potential of this approach is illustrated for the European Union's 28 member states (EU-28) through Monte Carlo simulations. High-rate contact stabilization captures the highest amount of COD (66-86 g COD person equivalent(-1) day(-1) in 60% of the iterations). Combined with thermal hydrolysis, this would lead to a VFA-yield of 23-44 g COD person equivalent(-1) day(-1). Upgrading VFA generated by the EU-28 would allow, in 60% of the simulations, for a yearly production of 0.2-2.0 megatonnes of esters, 0.7-1.4 megatonnes of polyhydroxyalkanoates or 0.6-2.2 megatonnes of microbial protein substituting, respectively, 20-273%, 70-140% or 21-72% of their global counterparts (i.e., petrochemical-based esters, bioplastics or fishmeal). From these flows, we conclude that sewage has a strong potential as biorefinery feedstock, although research is needed to enhance capture, fermentation and upgrading efficiencies. These developments need to be supported by economic/environmental analyses and policies that incentivize a more sustainable management of our resources.
Keywords: A1 Journal article; Sustainable Energy, Air and Water Technology (DuEL)
DOI: 10.1021/ACS.EST.7B05712
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“Activation of CO2on Copper Surfaces: The Synergy between Electric Field, Surface Morphology, and Excess Electrons”. Jafarzadeh A, Bal KM, Bogaerts A, Neyts EC, Journal Of Physical Chemistry C 124, 6747 (2020). http://doi.org/10.1021/acs.jpcc.0c00778
Abstract: In this work, we use density functional theory calculations to study the combined effect of external electric fields, surface morphology, and surface charge on CO2 activation over Cu(111), Cu(211), Cu(110), and Cu(001) surfaces. We observe that the binding energy of the CO2 molecule on Cu surfaces increases significantly upon increasing the applied electric field strength. In addition, rougher surfaces respond more effectively to the presence of the external electric field toward facilitating the formation of a carbonate-like CO2 structure and the transformation of the most stable adsorption mode from physisorption to chemisorption. The presence of surface charges further strengthens the electric field effect and consequently causes an improved bending of the CO2 molecule and C−O bond length elongation. On the other hand, a net charge in the absence of an externally applied electric field shows only a marginal effect on CO2 binding. The chemisorbed CO2 is more stable and further activated when the effects of an external electric field, rough surface, and surface charge are combined. These results can help to elucidate the underlying factors that control CO2 activation in heterogeneous and plasma catalysis, as well as in electrochemical processes.
Keywords: A1 Journal article; Engineering sciences. Technology; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 3.7
DOI: 10.1021/acs.jpcc.0c00778
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“Aptasensing of chloramphenicol in the presence of its analogues : reaching the maximum residue limit”. Pilehvar S, Mehta J, Dardenne F, Robbens J, Blust R, De Wael K, Analytical chemistry 84, 6753 (2012). http://doi.org/10.1021/AC3012522
Abstract: A novel label-free folding induced aptamer-based electrochemical biosensor for the detection of chloramphenicol (CAP) in the presence of its analogues has been developed. CAP is a broad-spectrum antibiotic which has lost its favor due to its serious adverse toxic effects on human health. Aptamers are artificial nucleic acid ligands (ssDNA or RNA) able to specifically recognize a target such as CAP. In this article, the aptamers are fixed onto a gold electrode surface by a self-assembly approach. In the presence of CAP, the unfolded ssDNA on the electrode surface changes to a hairpin structure bringing the target molecules close to the surface and trigger electron transfer. Detection limits were determined to be 1.6×10-9 mol L-1. In addition, thiamphenicol (TAP) and florfenicol (FF), antibiotics with a similar structure to CAP, did not influence the performance of the aptasensor, suggesting a good selectivity of the CAP-aptasensor. Simplicity and lower detection limit (because of the home-selected aptamers) make that the electrochemical aptasensor is suitable for practical use in the detection of CAP in milk samples.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 6.32
Times cited: 68
DOI: 10.1021/AC3012522
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“Films of filled single-wall carbon nanotubes as a new material for high-performance air-sustainable transparent conductive electrodes operating in a wide spectral range”. Tonkikh AA, Tsebro VI, Obraztsova EA, Rybkovskiy DV, Orekhov AS, Kondrashov II, Kauppinen EI, Chuvilin AL, Obraztsova ED, Nanoscale 11, 6755 (2019). http://doi.org/10.1039/C8NR10238D
Abstract: In this paper we show the advantages of transparent high conductive films based on filled single-wall carbon nanotubes. The nanotubes with internal channels filled with acceptor molecules (copper chloride or iodine) form networks demonstrating significantly improved characteristics. Due to the charge transfer between the nanotubes and filler, the doped-nanotube films exhibit a drop in electrical sheet resistance of an order of magnitude together with a noticeable increase of film transparency in the visible and near-infrared spectral range. The thermoelectric power measurements show a significant improvement of air-stability of the nanotube network in the course of the filling procedure. For the nanotube films with an initial transparency of 87% at 514 nm and electrical sheet resistance of 862 Ohm sq(-1) we observed an improvement of transparency up to 91% and a decrease of sheet resistance down to 98 Ohm sq(-1). The combination of the nanotube synthesis technique and molecules for encapsulation has been optimized for applications in optoelectronics.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 7.367
Times cited: 2
DOI: 10.1039/C8NR10238D
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“Real-time FO-SPR monitoring of solid-phase DNAzyme cleavage activity for cutting-edge biosensing”. Peeters B, Daems D, Van der Donck T, Delport F, Lammertyn J, ACS applied materials and interfaces 11, 6759 (2019). http://doi.org/10.1021/ACSAMI.8B18756
Abstract: DNA nanotechnology has a great potential in biosensor design including nanostructuring of the biosensor surface through DNA origami, target recognition by means of aptamers, and DNA-based signal amplification strategies. In this paper, we use DNA nanotechnology to describe for the first time the concept of real-time solid-phase monitoring of DNAzyme cleavage activity for the detection of specific single-stranded DNA (ssDNA) with a fiber optic surface plasmon resonance (FO-SPR) biosensor. Hereto, we first developed a robust ligation strategy for the functionalization of the FO-SPR biosensing surface with ssDNA-tethered gold nanoparticles, serving as the substrate for the DNAzyme. Next, we established a relation between the SPR signal change, due to the cleavage activity of the 10–23 DNAzyme, and the concentration of the DNAzyme, showing faster cleavage kinetics for higher DNAzyme concentrations. Finally, we implemented this generic concept for biosensing of ssDNA target in solution. Hereto, we designed a DNAzyme–inhibitor complex, consisting of an internal loop structure complementary to the ssDNA target, that releases active DNAzyme molecules in a controlled way as a function of the target concentration. We demonstrated reproducible target detection with a theoretical limit of detection of 1.4 nM, proving that the presented ligation strategy is key to a universal DNAzyme-based FO-SPR biosensing concept with promising applications in the medical and agrofood sector.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1021/ACSAMI.8B18756
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“Assessing the origin and fate of CR, Ni, Cu, Zn, Ph, and V in industrial polluted soil by combined microspectroscopic techniques and bulk extraction methods”. Terzano R, Spagnuolo M, Vekemans B, de Nolf W, Janssens K, Falkenberg G, Ruggiero P, Environmental science &, technology 41, 6762 (2007). http://doi.org/10.1021/ES070260H
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Times cited: 61
DOI: 10.1021/ES070260H
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“Reweighted Jarzynski sampling : acceleration of rare events and free energy calculation with a bias potential learned from nonequilibrium work”. Bal KM, Journal Of Chemical Theory And Computation 17, 6766 (2021). http://doi.org/10.1021/ACS.JCTC.1C00574
Abstract: We introduce a simple enhanced sampling approach for the calculation of free energy differences and barriers along a one-dimensional reaction coordinate. First, a small number of short nonequilibrium simulations are carried out along the reaction coordinate, and the Jarzynski equality is used to learn an approximate free energy surface from the nonequilibrium work distribution. This free energy estimate is represented in a compact form as an artificial neural network and used as an external bias potential to accelerate rare events in a subsequent molecular dynamics simulation. The final free energy estimate is then obtained by reweighting the equilibrium probability distribution of the reaction coordinate sampled under the influence of the external bias. We apply our reweighted Jarzynski sampling recipe to four processes of varying scales and complexities.spanning chemical reaction in the gas phase, pair association in solution, and droplet nucleation in supersaturated vapor. In all cases, we find reweighted Jarzynski sampling to be a very efficient strategy, resulting in rapid convergence of the free energy to high precision.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 5.245
DOI: 10.1021/ACS.JCTC.1C00574
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“Novel optical photothermal infrared (O-PTIR) spectroscopy for the noninvasive characterization of heritage glass-metal objects”. Marchetti A, Beltran V, Nuyts G, Borondics F, De Meyer S, Van Bos M, Jaroszewicz J, Otten E, Debulpaep M, De Wael K, Science Advances 8, eabl6769 (2022). http://doi.org/10.1126/SCIADV.ABL6769
Abstract: Optical photothermal infrared (O-PTIR) is a recently developed molecular spectroscopy technique that allows to noninvasively obtain chemical information on organic and inorganic samples at a submicrometric scale. The high spatial resolution (approximate to 450 nm), lack of sample preparation, and comparability of the spectral results to traditional Fourier transform infrared spectroscopy make it a promising candidate for the analysis of cultural heritage. In this work, the potential of O-PTIR for the noninvasive characterization of small heritage objects (few cubic centimeters) is demonstrated on a series of degraded 16th century brass and glass decorative elements. These small and challenging samples, typically encountering limitations with existing noninvasive methods such as macroscopic x-ray powder diffraction and mu Raman, were successfully characterized by O-PTIR, ultimately identifying the markers of glass-induced metal corrosion processes. The results clearly demonstrate how O-PTIR can be easily implemented in a noninvasive multianalytical strategy for the study of heritage materials, making it a fundamental tool for cultural heritage analyses.
Keywords: A1 Journal article; Engineering sciences. Technology; Antwerp Electrochemical and Analytical Sciences Lab (A-Sense Lab); Antwerp X-ray Imaging and Spectroscopy (AXIS)
Impact Factor: 13.6
DOI: 10.1126/SCIADV.ABL6769
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“3D Magnetic Induction Maps of Nanoscale Materials Revealed by Electron Holographic Tomography”. Wolf D, Rodriguez LA, Béché, A, Javon E, Serrano L, Magen C, Gatel C, Lubk A, Lichte H, Bals S, Van Tendeloo G, Fernández-Pacheco A, De Teresa JM, Snoeck E, Chemistry of materials 27, 6771 (2015). http://doi.org/10.1021/acs.chemmater.5b02723
Abstract: The investigation of three-dimensional (3D) ferromagnetic nanoscale materials constitutes one of the key research areas of the current magnetism roadmap, and carries great potential to impact areas such as data storage, sensing and biomagnetism. The properties of such nanostructures are closely connected with their 3D magnetic nanostructure, making their determination highly valuable. Up to now, quantitative 3D maps providing both the internal magnetic and electric configuration of the same specimen with high spatial resolution are missing. Here, we demonstrate the quantitative 3D reconstruction of the dominant axial component of the magnetic induction and electrostatic potential within a cobalt nanowire (NW) of 100 nm in diameter with spatial resolution below 10 nanometers by applying electron holographic tomography. The tomogram was obtained using a dedicated TEM sample holder for acquisition, in combination with advanced alignment and tomographic reconstruction routines. The powerful approach presented here is widely applicable to a broad range of 3D magnetic nanostructures and may trigger the progress of novel spintronic non-planar nanodevices.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 50
DOI: 10.1021/acs.chemmater.5b02723
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“Metal-assisted secondary ion mass spectrometry: the influence of Ag and Au deposition on molecular ion yields”. Adriaensen L, Vangaever F, Gijbels R, Analytical chemistry 76, 6777 (2004). http://doi.org/10.1021/ac049108d
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 6.32
Times cited: 67
DOI: 10.1021/ac049108d
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“Grain boundaries as a diffusion-limiting factor in lithium-rich NMC cathodes for high-energy lithium-ion batteries”. Abakumov AM, Li C, Boev A, Aksyonov DA, Savina AA, Abakumova TA, Van Tendeloo G, Bals S, ACS applied energy materials 4, 6777 (2021). http://doi.org/10.1021/ACSAEM.1C00872
Abstract: High-energy lithium-rich layered transition metal oxides are capable of delivering record electrochemical capacity and energy density as positive electrodes for Li-ion batteries. Their electrochemical behavior is extremely complex due to sophisticated interplay between crystal structure, electronic structure, and defect structure. Here we unravel an extra level of this complexity by revealing that the most typical representative Li1.2Ni0.13Mn0.54Co0.13O2 material, prepared by a conventional coprecipitation technique with Na2CO3 as a precipitating agent, contains abundant coherent (001) grain boundaries with a Na-enriched P2-structured block due to segregation of the residual sodium traces. The trigonal prismatic oxygen coordination of Na triggers multiple nanoscale twinning, giving rise to incoherent (104) boundaries. The cationic layers at the (001) grain boundaries are filled with transition metal cations being Mn-depleted and Co-enriched; this makes them virtually not permeable for the Li+ cations, and therefore they negatively influence the Li diffusion in and out of the spherical agglomerates. These results demonstrate that besides the mechanisms intrinsic to the crystal and electronic structure of Li-rich cathodes, their rate capability might also be depreciated by peculiar microstructural aspects. Dedicated engineering of grain boundaries opens a way for improving inherently sluggish kinetics of these materials.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Times cited: 4
DOI: 10.1021/ACSAEM.1C00872
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“Spontaneous Chirality Evolved at the Au–Ag Interface in Plasmonic Nanorods”. Sa J, Hu N, Heyvaert W, Van Gordon K, Li H, Wang L, Bals S, Liz-Marzán LM, Ni W, Chemistry of materials (2023). http://doi.org/10.1021/acs.chemmater.3c01044
Abstract: Chiral ligands are considered a required ingredient during the synthesis of dissymmetric plasmonic metal nanocrystals. The mechanism behind the generation of chiral structures involves the formation of high Miller index chiral facets, induced by the adsorption of such chiral ligands. We found however that, chirality can also evolve spontaneously, without the involvement of any chiral ligands, during the co-deposition of Au and Ag on Au nanorods. When using a specific Au/Ag ratio, phase segregation of the two metals leads to an interface within the obtained AuAg shell, which can be exposed by removing the Ag component via oxidative etching. Although a close-to-racemic mixture of chiral Au nanorods with right and left handedness is found in solution, electron tomography analysis evidences left- and righthanded helicities, both at the Au-Ag interface and at the exposed surface of Au NRs after Ag etching. The helicity profile of the NRs indicates dominating inclination angles in a range from 30° to 60°. Single-particle optical characterization also reveals random handedness in the plasmonic response of individual nanorods. We hypothesize that, the origin of chirality is related with symmetry breaking during the co-deposition of Au and Ag, through an initial perturbation in a small region on the Au-Ag interface that eventually leads to chiral segregation throughout the nanocrystal.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 8.6
DOI: 10.1021/acs.chemmater.3c01044
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“Electrorheological fluids with high shear stress based on wrinkly tin titanyl oxalate”. Wu J, Zhang L, Xin X, Zhang Y, Wang H, Sun A, Cheng Y, Chen X, Xu G, ACS applied materials and interfaces 10, 6785 (2018). http://doi.org/10.1021/ACSAMI.8B00869
Abstract: Electrorheological (ER) fluids are considered as a type of smart fluids because their rheological characteristics can be altered through an electric field. The discovery of giant ER effect revived the researchers' interest in the ER technological area. However, the poor stability including the insufficient dynamic shear stress, the large leakage current density, and the sedimentation tendency still hinders their practical applications. Herein, we report a facile and scalable coprecipitation method for synthesizing surfactant-free tin titanyl oxalate (TTO) particles with tremella-like wrinkly microstructure (W-TTO). The W-TTO-based ER fluids exhibit enhanced ER activity compared to that of the pristine TTO because of the improved wettability between W-TTO and the silicone oil. In addition, the static yield stress and leakage current of W-TTO ER fluids also show a fine time stability during the 30 day tests. More importantly, the dynamic shear stress of W-TTO ER fluids can remain stable throughout the shear rate range, which is valuable for their use in engineering applications. The results in this work provided a promising strategy to solving the long-standing problem of ER fluid stability. Moreover, this convenient route of synthesis may be considered a green approach for the mass production of giant ER materials.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 7.504
Times cited: 7
DOI: 10.1021/ACSAMI.8B00869
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“Three-dimensional trace element analysis by confocal X-ray microfluorescence imaging”. Vincze L, Vekemans B, Brenker FE, Falkenberg G, Rickers K, Somogyi A, Kersten M, Adams F, Analytical chemistry 76, 6786 (2004). http://doi.org/10.1021/AC049274L
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1021/AC049274L
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