“Hole-induced spontaneous mutual annihilation of dislocation pairs”. Wu Y, Chen G, Yu J, Wang D, Ma C, Li C, Pennycook SJ, Yan Y, Wei S-H, The journal of physical chemistry letters 10, 7421 (2019). http://doi.org/10.1021/ACS.JPCLETT.9B02918
Abstract: Dislocations are always observed during crystal growth, and it is usually desirable to reduce the dislocation density in high-quality crystals. Here, the annihilation process of the 30 degrees Shockley partial dislocation pairs in CdTe is studied by first-principles calculations. We found that the dislocations can glide relatively easily due to the weak local bonding. Our systematic study of the slipping mechanism of the dislocations suggests that the energy barrier for the annihilation process is low. Band structure calculations reveal that the band bending caused by the charge transfer between the two dislocation cores depends on the core-core distance. A simple linear model is proposed to describe the mechanism of formation of the dislocation pair. More importantly, we demonstrate that hole injection can affect the core structure, increase the mobility, and eventually trigger a spontaneous mutual annihilation, which could be employed as a possible facile way to reduce the dislocation density.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 9.353
DOI: 10.1021/ACS.JPCLETT.9B02918
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“How membrane lipids influence plasma delivery of reactive oxygen species into cells and subsequent DNA damage : an experimental and computational study”. Van der Paal J, Hong S-H, Yusupov M, Gaur N, Oh J-S, Short RD, Szili EJ, Bogaerts A, Physical chemistry, chemical physics 21, 19327 (2019). http://doi.org/10.1039/C9CP03520F
Abstract: The mechanisms of plasma in medicine are broadly attributed to plasma-derived reactive oxygen and nitrogen species (RONS). In order to exert any intracellular effects, these plasma-derived RONS must first traverse a major barrier in the cell membrane. The cell membrane lipid composition, and thereby the magnitude of this barrier, is highly variable between cells depending on type and state (e.g. it is widely accepted that healthy and cancerous cells have different membrane lipid compositions). In this study, we investigate how plasma-derived RONS interactions with lipid membrane components can potentially be exploited in the future for treatment of diseases. We couple phospholipid vesicle experiments, used as simple cell models, with molecular dynamics (MD) simulations of the lipid membrane to provide new insights into how the interplay between phospholipids and cholesterol may influence the response of healthy and diseased cell membranes to plasma-derived RONS. We focus on the (i) lipid tail saturation degree, (ii) lipid head group type, and (iii) membrane cholesterol fraction. Using encapsulated molecular probes, we study the influence of the above membrane components on the ingress of RONS into the vesicles, and subsequent DNA damage. Our results indicate that all of the above membrane components can enhance or suppress RONS uptake, depending on their relative concentration within the membrane. Further, we show that higher RONS uptake into the vesicles does not always correlate with increased DNA damage, which is attributed to ROS reactivity and lifetime. The MD simulations indicate the multifactorial chemical and physical processes at play, including (i) lipid oxidation, (ii) lipid packing, and (iii) lipid rafts formation. The methods and findings presented here provide a platform of knowledge that could be leveraged in the development of therapies relying on the action of plasma, in which the cell membrane and oxidative stress response in cells is targeted.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 4.123
Times cited: 1
DOI: 10.1039/C9CP03520F
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“Mechanistic studies of gas reactions with multicomponent solids : what can we learn by combining NAP XPS and atomic resolution STEM/EDX?”.Sirotina AP, Callaert C, Volykhov AA, Frolov AS, Sanchez-Barriga J, Knop-Gericke A, Hadermann J, Yashina LV, The journal of physical chemistry: C : nanomaterials and interfaces 123, 26201 (2019). http://doi.org/10.1021/ACS.JPCC.9B05052
Abstract: Rapid development of experimental techniques has enabled real time studies of solid gas reactions at the level reaching the atomic scale. In the present paper, we focus on a combination of atomic resolution STEM/EDX, which visualizes the reaction zone, and near ambient pressure (NAP) XPS, which collects information for a surface layer of variable thickness under reaction conditions. We compare the behavior of two affined topological insulators, Bi2Te3 and Sb2Te3. We used a simple reaction with molecular oxygen occurring at 298 K, which is of practical importance to avoid material degradation. Despite certain limitations, a combination of in situ XPS and ex situ cross-sectional STEM/EDX allowed us to obtain a self-consistent picture of the solid gas reaction mechanism for oxidation of Sb2Te3 and Bi2Te3 crystals, which includes component redistribution between the oxide and the subsurface layer and Te segregation with formation of a thin ordered layer at the interface. The process is multistep in case of both compounds. At the very beginning of the oxidation process the reactivity is determined by the energy benefit of the corresponding element oxygen bond formation. Further in the oxidation process, the behavior of these two compounds becomes similar and features component redistribution between the oxide and the subsurface layer.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 4.536
DOI: 10.1021/ACS.JPCC.9B05052
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“Plasma-enabled catalyst-free conversion of ethanol to hydrogen gas and carbon dots near room temperature”. Zhou R, Zhou R, Xian Y, Fang Z, Lu X, Bazaka K, Bogaerts A, Ostrikov K(K), Chemical Engineering Journal 382, 122745 (2020). http://doi.org/10.1016/J.CEJ.2019.122745
Abstract: Selective conversion of bio-renewable ethanol under mild conditions especially at room temperature remains a major challenge for sustainable production of hydrogen and valuable carbon-based materials. In this study, adaptive non-thermal plasma is applied to deliver pulsed energy to rapidly and selectively reform ethanol in the absence of a catalyst. Importantly, the carbon atoms in ethanol that would otherwise be released into the environment in the form of CO or CO2 are effectively captured in the form of carbon dots (CDs). Three modes of non-thermal spark plasma discharges, i.e. single spark mode (SSM), multiple spark mode (MSM) and gliding spark mode (GSM), provide additional flexibility in ethanol reforming by controlling the processes of energy transfer and distribution, thereby affecting the flow rate, gas content, and energy consumption in H-2 production. A favourable combination of low temperature (< 40 degrees C), attractive conversion rate (gas flow rate of similar to 120 mL/min), high hydrogen yield (H-2 content > 90%), low energy consumption (similar to 0.96 kWh/m(3) H-2) and the effective generation of photoluminescent CDs (which are applicable for bioimaging or biolabelling) in the MSM indicate that the proposed strategy may offer a new carbon-negative avenue for comprehensive utilization of alcohols and mitigating the increasingly severe energy and environmental issues.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 15.1
Times cited: 20
DOI: 10.1016/J.CEJ.2019.122745
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“Reactivity and stability of plasma-generated oxygen and nitrogen species in buffered water solution: a computational study”. Heirman P, Van Boxem W, Bogaerts A, Physical chemistry, chemical physics 21, 12881 (2019). http://doi.org/10.1039/C9CP00647H
Abstract: Plasma-treated liquids have great potential for biomedical applications. However, insight into the underlying mechanisms and the exact chemistry is still scarce. In this study, we present the combination of a 0D chemical kinetics and a 2D fluid dynamics model to investigate the plasma treatment of a buffered water solution with the kINPen (R) plasma jet. Using this model, we calculated the gas and liquid flow profiles and the transport and chemistry of all species in the gas and the liquid phase. Moreover, we evaluated the stability of the reactive oxygen and nitrogen species after plasma treatment. We found that of all species, only H2O2, HNO2/NO2-, and HNO3/NO3- are stable in the buffered solution after plasma treatment. This is because both their production and loss processes in the liquid phase are dependent on short-lived radicals (e.g. OH, NO, and NO2). Apart from some discrepancy in the absolute values of the concentrations, which can be explained by the model, all general trends and observations in our model are in qualitative agreement with experimental data and literature.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 4.123
Times cited: 7
DOI: 10.1039/C9CP00647H
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“Vertical van der Waals heterostructure of single layer InSe and SiGe”. Eren I, Ozen S, Sozen Y, Yagmurcukardes M, Sahin H, The journal of physical chemistry: C : nanomaterials and interfaces 123, 31232 (2019). http://doi.org/10.1021/ACS.JPCC.9B06404
Abstract: We present a first-principles investigation on the stability, electronic structure, and mechanical response of ultrathin heterostructures composed of single layers of InSe and SiGe. First, by performing total energy optimization and phonon calculations, we show that single layers of InSe and SiGe can form dynamically stable heterostructures in 12 different stacking types. Valence and conduction band edges of the heterobilayers form a type-I heterojunction having a tiny band gap ranging between 0.09 and 0.48 eV. Calculations on elastic-stiffness tensor reveal that two mechanically soft single layers form a heterostructure which is stiffer than the constituent layers because of relatively strong interlayer interaction. Moreover, phonon analysis shows that the bilayer heterostructure has highly Raman active modes at 205.3 and 43.7 cm(-1), stemming from the out-of-plane interlayer mode and layer breathing mode, respectively. Our results show that, as a stable type-I heterojunction, ultrathin heterobilayer of InSe/SiGe holds promise for nanoscale device applications.
Keywords: A1 Journal article; Engineering sciences. Technology; Condensed Matter Theory (CMT)
Impact Factor: 4.536
DOI: 10.1021/ACS.JPCC.9B06404
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“Assessment of sulfur-functionalized MXenes for li-ion battery applications”. Siriwardane EMD, Demiroglu I, Sevik C, Peeters FM, Çakir D, Journal Of Physical Chemistry C 124, 21293 (2020). http://doi.org/10.1021/ACS.JPCC.0C05287
Abstract: The surface termination of MXenes greatly determines the electrochemical properties and ion kinetics on their surfaces. So far, hydroxyl-, oxygen-, and fluorine-terminated MXenes have been widely studied for energy storage applications. Recently, sulfur-functionalized MXene structures, which possess low diffusion barriers, have been proposed as candidate materials to enhance battery performance. We performed first-principles calculations on the structural, stability, electrochemical, and ion dynamic properties of Li-adsorbed sulfur-functionalized groups 3B, 4B, 5B, and 6B transition-metal (M)-based MXenes (i.e., M2CS2 with M = Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W). We performed phonon calculations, which indicated that all of the above M2CS2 MXenes, except for Sc, are dynamically stable at T = 0 K. The ground-state structure of each M2CS2 monolayer depends on the type of M atom. For instance, while sulfur prefers to sit at the FCC site on Ti2CS2, it occupies the HCP site of Cr-based MXene. We determined the Li adsorption configurations at different concentrations using the cluster expansion method. The highest maximum open-circuit voltages were computed for the group 4B element (i.e., Ti, Zr, and Hf)-based M2CS2, which are larger than 2.1 V, while their average voltages are approximately 1 V. The maximum voltage for the group 6B element (i.e., Cr, Mo, W)-based M2CS2 is less than 1 V, and the average voltage is less than 0.71 V. We found that S functionalization is helpful for capacity improvements over the O-terminated MXenes. In this respect, the computed storage gravimetric capacity may reach up to 417.4 mAh/g for Ti2CS2 and 404.5 mAh/g for V2CS2. Ta-, Cr-, Mo-, and W-based M2CS2 MXenes show very low capacities, which are less than 100 mAh/g. The Li surface diffusion energy barriers for all of the considered MXenes are less than 0.22 eV, which is favorable for high charging and discharging rates. Finally, ab initio molecular dynamic simulations performed at 400 K and bond-length analysis with respect to Li concentration verify that selected promising systems are robust against thermally induced perturbations that may induce structural transformations or distortions and undesirable Li release.
Keywords: A1 Journal article; Engineering sciences. Technology; Condensed Matter Theory (CMT)
Impact Factor: 3.7
Times cited: 24
DOI: 10.1021/ACS.JPCC.0C05287
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“Boosting biomolecular interactions through DNA origami nano-tailored biosensing interfaces”. Rutten I, Daems D, Lammertyn J, Journal Of Materials Chemistry B 8, 3606 (2020). http://doi.org/10.1039/C9TB02439E
Abstract: The interaction between a bioreceptor and its target is key in developing sensitive, specific and robust diagnostic devices. Suboptimal interbioreceptor distances and bioreceptor orientation on the sensor surface, resulting from uncontrolled deposition, impede biomolecular interactions and lead to a decreased biosensor performance. In this work, we studied and implemented a 3D DNA origami design, for the first time comprised of assay specifically tailored anchoring points for the nanostructuring of the bioreceptor layer on the surface of disc-shaped microparticles in the continuous microfluidic environment of the innovative EvalutionTM platform. This bioreceptor immobilization strategy resulted in the formation of a less densely packed surface with reduced steric hindrance and favoured upward orientation. This increased bioreceptor accessibility led to a 4-fold enhanced binding kinetics and a 6-fold increase in binding efficiency compared to a directly immobilized non-DNA origami reference system. Moreover, the DNA origami nanotailored biosensing concept outperformed traditional aptamer coupling with respect to limit of detection (11 × improved) and signal-to-noise ratio (2.5 × improved) in an aptamer-based sandwich bioassay. In conclusion, our results highlight the potential of these DNA origami nanotailored surfaces to improve biomolecular interactions at the sensing surface, thereby increasing the overall performance of biosensing devices. The combination of the intrinsic advantages of DNA origami together with a smart design enables bottom-up nanoscale engineering of the sensor surface, leading towards the next generation of improved diagnostic sensing devices.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 7
Times cited: 2
DOI: 10.1039/C9TB02439E
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“Control of C3N4 and C4N3 carbon nitride nanosheets' electronic and magnetic properties through embedded atoms”. Bafekry A, Stampfl C, Akgenc B, Ghergherehchi M, Physical Chemistry Chemical Physics 22, 2249 (2020). http://doi.org/10.1039/C9CP06031F
Abstract: In the present work, the effect of various embedded atom impurities on tuning electronic and magnetic properties of C3N4 and C4N3 nanosheets have been studied using first-principles calculations. Our calculations show that C3N4 is a semiconductor and it exhibits extraordinary electronic properties such as dilute-magnetic semiconductor (with H, F, Cl, Be, V, Fe and Co); metal (with N, P, Mg and Ca), half-metal (with Li, Na, K, Al, Sc, Cr, Mn, and Cu) and semiconductor (with O, S, B, C, Si, Ti, Ni and Zn) with the band gaps in the range of 0.3-2.0 eV depending on the species of embedded atom. The calculated electronic properties reveal that C4N3 is a half-metal and it retains half-metallic character with embedded H, O, S, F, B, N, P, Be, Mg, Al, Sc, V, Fe, Ni and Zn atoms. The substitution of Cl, C, Cr and Mn atoms create ferromagnetic-metal character in the C4N3 nanosheet, embedded Co and Cu atoms exhibit a dilute-magnetic semiconductor nature, and embedded Ti atoms result in the system becoming a semiconductor. Therefore, our results reveal the fact that the band gap and magnetism can be modified or induced by various atom impurities, thus, offering effective possibilities to tune the electronic and magnetic properties of C3N4 and C4N3 nanosheets.
Keywords: A1 Journal article; Condensed Matter Theory (CMT)
Impact Factor: 3.3
Times cited: 18
DOI: 10.1039/C9CP06031F
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“Covalent immobilization of delipidated human serum albumin on poly(pyrrole-2-carboxylic) acid film for the impedimetric detection of perfluorooctanoic acid”. Moro G, Bottari F, Liberi S, Covaceuszach S, Cassetta A, Angelini A, De Wael K, Moretto LM, Bioelectrochemistry 134, 107540 (2020). http://doi.org/10.1016/J.BIOELECHEM.2020.107540
Abstract: The immobilization of biomolecules at screen printed electrodes for biosensing applications is still an open challenge. To enrich the toolbox of bioelectrochemists, graphite screen printed electrodes (G-SPE) were modified with an electropolymerized film of pyrrole-2-carboxilic acid (Py-2-COOH), a pyrrole derivative rich in carboxylic acid functional groups. These functionalities are suitable for the covalent immobilization of biomolecular recognition layers. The electropolymerization was first optimized to obtain stable and conductive polymeric films, comparing two different electrolytes: sodium dodecyl sulphate (SDS) and sodium perchlorate. The G-SPE modified with Py-2-COOH in 0.1 M SDS solution showed the required properties and were further tested. A proof-of-concept study for the development of an impedimetric sensor for perfluorooctanoic acid (PFOA) was carried out using the delipidated human serum albumin (hSA) as bioreceptor. The data interpretation was supported by size exclusion chromatography and small-angle X-ray scattering (SEC-SAXS) analysis of the bioreceptor-target complex and the preliminary results suggest the possibility to further develop this biosensing strategy for toxicological and analytical studies.
Keywords: A1 Journal article; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 5
DOI: 10.1016/J.BIOELECHEM.2020.107540
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“Do aptamers always bind? The need for a multifaceted analytical approach when demonstrating binding affinity between aptamer and low molecular weight compounds”. Bottari F, Daems E, de Vries A-M, Van Wielendaele P, Trashin S, Blust R, Sobott F, Madder A, Martins JC, De Wael K, Journal Of The American Chemical Society 142, jacs.0c08691 (2020). http://doi.org/10.1021/JACS.0C08691
Abstract: In this manuscript, we compare different analytical methodologies to validate or disprove the binding capabilities of aptamer sequences. This was prompted by the lack of a universally accepted and robust quality control protocol for the characterization of aptamer performances coupled with the observation of independent yet inconsistent data sets in the literature. As an example, we chose three aptamers with a reported affinity in the nanomolar range for ampicillin, a β-lactam antibiotic, used as biorecognition elements in several detection strategies described in the literature. Application of a well-known colorimetric assay based on aggregation of gold nanoparticles (AuNPs) yielded conflicting results with respect to the original report. Therefore, ampicillin binding was evaluated in solution using isothermal titration calorimetry (ITC), native nano-electrospray ionization mass spectrometry (native nESI-MS), and 1H-nuclear magnetic resonance spectroscopy (1H NMR). By coupling the thermodynamic data obtained with ITC with the structural information on the binding event given by native nESI-MS and 1H NMR we could verify that none of the ampicillin aptamers show any specific binding with their intended target. The effect of AuNPs on the binding event was studied by both ITC and 1H NMR, again without providing positive evidence of ampicillin binding. To validate the performance of our analytical approach, we investigated two well-characterized aptamers for cocaine/quinine (MN4), chosen for its nanomolar range affinity, and l-argininamide (1OLD) to show the versatility of our approach. The results clearly indicate the need for a multifaceted analytical approach, to unequivocally establish the actual detection potential and performance of aptamers aimed at small organic molecules.
Keywords: A1 Journal article; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Medical Biochemistry
Impact Factor: 15
DOI: 10.1021/JACS.0C08691
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“Embedding of atoms into the nanopore sites of the C₆N₆, and C₆N₈, porous carbon nitride monolayers with tunable electronic properties”. Bafekry A, Stampfl C, Akgenc B, Mortazavi B, Ghergherehchi M, Nguyen CV, Physical Chemistry Chemical Physics 22, 6418 (2020). http://doi.org/10.1039/D0CP00093K
Abstract: Using first-principles calculations, we study the effect of embedding various atoms into the nanopore sites of both C6N6 and C6N8 monolayers. Our results indicate that the embedded atoms significantly affect the electronic and magnetic properties of C6N6 and C6N8 monolayers and lead to extraordinary and multifarious electronic properties, such as metallic, half-metallic, spin-glass semiconductor and dilute-magnetic semiconductor behaviour. Our results reveal that the H atom concentration dramatically affects the C6N6 monolayer. On increasing the H coverage, the impurity states also increase due to H atoms around the Fermi-level. C6N6 shows metallic character when the H atom concentration reaches 6.25%. Moreover, the effect of charge on the electronic properties of both Cr@C6N6 and C@C6N8 is also studied. Cr@C6N6 is a ferromagnetic metal with a magnetic moment of 2.40 mu(B), and when 0.2 electrons are added and removed, it remains a ferromagnetic metal with a magnetic moment of 2.57 and 2.77 mu(B), respectively. Interestingly, one can observe a semi-metal, in which the VBM and CBM in both spin channels touch each other near the Fermi-level. C@C6N8 is a semiconductor with a nontrivial band gap. When 0.2 electrons are removed, it remains metallic, and under excess electronic charge, it exhibits half-metallic behaviour.
Keywords: A1 Journal article; Condensed Matter Theory (CMT)
Impact Factor: 3.3
Times cited: 17
DOI: 10.1039/D0CP00093K
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“First-principles investigation of nonmetal doped single-layer BiOBr as a potential photocatalyst with a low recombination rate”. Obeid MM, Stampfl C, Bafekry A, Guan Z, Jappor HR, Nguyen C V, Naseri M, Hoat DM, Hieu NN, Krauklis AE, Tuan V Vu, Gogova D, Physical Chemistry Chemical Physics 22, 15354 (2020). http://doi.org/10.1039/D0CP02007A
Abstract: Nonmetal doping is an effective approach to modify the electronic band structure and enhance the photocatalytic performance of bismuth oxyhalides. Using density functional theory, we systematically examine the fundamental properties of single-layer BiOBr doped with boron (B) and phosphorus (P) atoms. The stability of the doped models is investigated based on the formation energies, where the substitutional doping is found to be energetically more stable under O-rich conditions than under Bi-rich ones. The results showed that substitutional doping of P atoms reduced the bandgap of pristine BiOBr to a greater extent than that of boron substitution. The calculation of the effective masses reveals that B doping can render the electrons and holes of pristine BiOBr lighter and heavier, respectively, resulting in a slower recombination rate of photoexcited electron-hole pairs. Based on the results of HOMO-LUMO calculations, the introduction of B atoms tends to increase the number of photocatalytically active sites. The top of the valence band and the conduction band bottom of the B doped BiOBr monolayer match well with the water redox potentials in an acidic environment. The absorption spectra propose that B(P) doping causes a red-shift. Overall, the results predict that nonmetal-doped BiOBr monolayers have a reduced bandgap, a slow recombination rate, more catalytically active sites, enhanced optical absorption edges, and reduced work functions, which will contribute to superior photocatalytic performance.
Keywords: A1 Journal article; Condensed Matter Theory (CMT)
Impact Factor: 3.3
Times cited: 18
DOI: 10.1039/D0CP02007A
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“Grain-boundary-induced strain and distortion in epitaxial bilayer MoS₂, lattice”. Mehta AN, Mo J, Pourtois G, Dabral A, Groven B, Bender H, Favia P, Caymax M, Vandervorst W, Journal Of Physical Chemistry C 124, 6472 (2020). http://doi.org/10.1021/ACS.JPCC.0C01468
Abstract: Grain boundaries between 60 degrees rotated and twinned crystals constitute the dominant type of extended line defects in two-dimensional transition metal dichalcogenides (2D MX2) when grown on a single crystalline template through van der Waals epitaxy. The two most common 60 degrees grain boundaries in MX2 layers, i.e., beta- and gamma-boundaries, introduce distinct distortion and strain into the 2D lattice. They impart a localized tensile or compressive strain on the subsequent layer, respectively, due to van der Waals coupling in bilayer MX2 as determined by combining atomic resolution electron microscopy, geometric phase analysis, and density functional theory. Based on these observations, an alternate route to strain engineering through controlling intrinsic van der Waals forces in homobilayer MX2 is proposed. In contrast to the commonly used external means, this approach enables the localized application of strain to tune the electronic properties of the 2D semiconducting channel in ultra-scaled nanoelectronic applications.
Keywords: A1 Journal article; Engineering sciences. Technology; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 3.7
Times cited: 2
DOI: 10.1021/ACS.JPCC.0C01468
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“Graphene hetero-multilayer on layered platinum mineral Jacutingaite (Pt₂HgSe₃): Van der Waals heterostructures with novel optoelectronic and thermoelectric performances”. Bafekry A, Obeid M, Nguyen C, Bagheri Tagani M, Ghergherehchi M, Journal Of Materials Chemistry A 8, 13248 (2020). http://doi.org/10.1039/D0TA02847A
Abstract: Motivated by the recent successful synthesis of the layered platinum mineral jacutingaite (Pt2HgSe3), we have studied the optoelectronic, mechanical, and thermoelectric properties of graphene hetero-multilayer on Pt(2)HgSe(3)monolayer (PHS) heterostructures (LG/PHS) by using first-principles calculations. PHS is a topological insulator with a band gap of about 160 meV with fully relativistic calculations; when graphene layers are stacked on PHS, a narrow band gap of similar to 10-15 meV opens. In the presence of gate-voltage and out-of plane strain,i.e.pressure, the electronic properties are modified; the Dirac-cone of graphene can be shifted upwards (downward) to a lower (higher) binding energy. The absorption spectrum shows two peaks, which are located around 216 nm (5.74 eV) and protracted to 490 nm (2.53 eV), indicating that PHS could absorb more visible light. Increasing the number of graphene layers on PHS has a positive impact on the UV-vis light absorption and gives a clear red-shift with enhanced absorption intensity. To investigate the electronic performance of the heterostructure, the electrical conductance and thermopower of a device composed of graphene layers and PHS is examined by a combination of DFT and Green function formalism. The number of graphene layers can significantly tune the thermopower and electrical conductance. This analysis reveals that the heterostructures not only significantly affect the electronic properties, but they can also be used as an efficient way to modulate the optic and thermoelectric properties.
Keywords: A1 Journal article; Engineering sciences. Technology; Condensed Matter Theory (CMT)
Impact Factor: 11.9
Times cited: 20
DOI: 10.1039/D0TA02847A
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“Insights into water permeation through hBN nanocapillaries by ab initio machine learning molecular dynamics simulations”. Ghorbanfekr H, Behler J, Peeters FM, Journal Of Physical Chemistry Letters 11, 7363 (2020). http://doi.org/10.1021/ACS.JPCLETT.0C01739
Abstract: Water permeation between stacked layers of hBN sheets forming 2D nanochannels is investigated using large-scale ab initio-quality molecular dynamics simulations. A high-dimensional neural network potential trained on density-functional theory calculations is employed. We simulate water in van der Waals nanocapillaries and study the impact of nanometric confinement on the structure and dynamics of water using both equilibrium and nonequilibrium methods. At an interlayer distance of 10.2 A confinement induces a first-order phase transition resulting in a well-defined AA-stacked bilayer of hexagonal ice. In contrast, for h < 9 A, the 2D water monolayer consists of a mixture of different locally ordered patterns of squares, pentagons, and hexagons. We found a significant change in the transport properties of confined water, particularly for monolayer water where the water-solid friction coefficient decreases to half and the diffusion coefficient increases by a factor of 4 as compared to bulk water. Accordingly, the slip-velocity is found to increase under confinement and we found that the overall permeation is dominated by monolayer water adjacent to the hBN membranes at extreme confinements. We conclude that monolayer water in addition to bilayer ice has a major contribution to water transport through 2D nanochannels.
Keywords: A1 Journal article; Engineering sciences. Technology; Condensed Matter Theory (CMT); Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 5.7
Times cited: 35
DOI: 10.1021/ACS.JPCLETT.0C01739
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“Integration of a photoelectrochemical cell in a flow system for quantification of 4-aminophenol with titanium dioxide”. Mendonça CD, Rahemi V, Hereijgers J, Breugelmans T, Machado SAS, De Wael K, Electrochemistry Communications 117, 106767 (2020). http://doi.org/10.1016/J.ELECOM.2020.106767
Abstract: The photoelectrochemical quantification of phenolic compounds such as hydroquinone (HQ) and 4-aminophenol (4-AP) is accomplished by integrating a photoelectrochemical cell into a flow injection analysis (FIA) setup. It is a well-known fact that during the electroanalysis of phenolic compounds, the electrode surface is susceptible to poisoning. However, electrode fouling can be reduced significantly by using the FIA system with periodic washing of the electrode. Reactive oxygen species (ROS), which are generated on the surface of TiO2 under UV light, can oxidize phenolic compounds such as 4-AP. The oxidized form of 4-AP is reduced back at the electrode surface, generating a measurable signal proportional to its concentration. The factors influencing the perfor-mance of the sensor, such as flow rate, applied potential for back reduction and pH, are investigated in detail. In the concentration range 0.0125-1.0 mu M, a linear correlation between the photocurrent and the concentration of 4-AP was observed with a sensitivity of 0.6 A M-1 cm(-2) and a limit of detection of 18 nM. A straightforward analytical methodology for the on-site, highly sensitive and low-cost quantification of phenolic compounds is presented, based on the use of TiO2 in a photoelectrochemical flow cell.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Applied Electrochemistry & Catalysis (ELCAT)
Impact Factor: 5.4
Times cited: 1
DOI: 10.1016/J.ELECOM.2020.106767
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“Modulating the electro-optical properties of doped C₃N monolayers and graphene bilayersviamechanical strain and pressure”. Bafekry A, Nguyen C, Obeid MM, Ghergherehchi M, New Journal Of Chemistry 44, 15785 (2020). http://doi.org/10.1039/D0NJ03340E
Abstract: In this work, we investigated systematically the electronic and optical properties of B doped C3N monolayers as well as B and N doped graphene bilayers (BN-Gr@2L). We found that the doping of B atoms leads to an enlarged band gap of the C3N monolayer and when the dopant concentration reaches 12.5%, an indirect-to-direct band gap switching occurs. In addition, with co-doping of B and N atoms on the graphene monolayer in the hexagonal configuration, an electronic transition from semi-metal to semiconductor occurs. Our optical results for B-C3N show a broad absorption spectrum in a wide visible range starting from 400 nm to 1000 nm with strong absorption intensity, making it a suitable candidate for nanoelectronic and optoelectronic applications. Interestingly, a transition from semi-metal to semiconductor emerges in the graphene monolayer with doping of B and N atoms. Furthermore, our results demonstrate that the in-plane strain and out-of-plane strain (pressure) can modulate the band gap of the BN-Gr@2L. The controllable electronic properties and optical features of the doped graphene bilayer by strain engineering may facilitate their practical performance for various applications in future.
Keywords: A1 Journal article; Condensed Matter Theory (CMT)
Impact Factor: 3.3
Times cited: 7
DOI: 10.1039/D0NJ03340E
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“Molecular fluorescence imaging spectroscopy for mapping low concentrations of red lake pigments : Van Gogh's painting The Olive Orchard”. Dooley KA, Chieli A, Romani A, Legrand S, Miliani C, Janssens K, Delaney JK, Angewandte Chemie-International Edition (2020). http://doi.org/10.1002/ANIE.201915490
Abstract: Vincent van Gogh used fugitive red lake pigments that have faded in some paintings. Mapping their distribution is key to understanding how his paintings have changed with time. While red lake pigments can be identified from microsamples, in situ identification and mapping remain challenging. This paper explores the ability of molecular fluorescence imaging spectroscopy to identify and, more importantly, map residual non-degraded red lakes. The high sensitivity of this method enabled identification of the emission spectra of eosin (tetrabromine fluorescein) lake mixed with lead or zinc white at lower concentrations than elemental X-ray fluorescence (XRF) spectroscopy used on account of bromine. The molecular fluorescence mapping of residual eosin and two carmine red lakes in van Gogh's The Olive Orchard is demonstrated and compared with XRF imaging spectroscopy. The red lakes are consistent with the composition of paint tubes known to have been used by van Gogh.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 16.6
Times cited: 2
DOI: 10.1002/ANIE.201915490
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“Nitrogen fixation with water vapor by nonequilibrium plasma : toward sustainable ammonia production”. Gorbanev Y, Vervloessem E, Nikiforov A, Bogaerts A, Acs Sustainable Chemistry &, Engineering 8, 2996 (2020). http://doi.org/10.1021/ACSSUSCHEMENG.9B07849
Abstract: Ammonia is a crucial nutrient used for plant growth and as a building block in the pharmaceutical and chemical industry, produced via nitrogen fixation of the ubiquitous atmospheric N2. Current industrial ammonia production relies heavily on fossil resources, but a lot of work is put into developing nonfossil-based pathways. Among these is the use of nonequilibrium plasma. In this work, we investigated water vapor as a H source for nitrogen fixation into NH3 by nonequilibrium plasma. The highest selectivity toward NH3 was observed with low amounts of added H2O vapor, but the highest production rate was reached at high H2O vapor contents. We also studied the role of H2O vapor and of the plasma-exposed liquid H2O in nitrogen fixation by using isotopically labeled water to distinguish between these two sources of H2O. We show that added H2O vapor, and not liquid H2O, is the main source of H for NH3 generation. The studied catalyst- and H2-free method offers excellent selectivity toward NH3 (up to 96%), with energy consumption (ca. 95–118 MJ/mol) in the range of many plasma-catalytic H2-utilizing processes.
Keywords: A1 Journal article; Engineering sciences. Technology; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 8.4
Times cited: 14
DOI: 10.1021/ACSSUSCHEMENG.9B07849
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“Novel 2-naphthyl substituted zinc naphthalocyanine : synthesis, optical, electrochemical and spectroelectrochemical properties”. Dubinina TV, Moiseeva EO, Astvatsaturov DA, Borisova NE, Tarakanov PA, Trashin SA, De Wael K, Tomilova LG, New Journal Of Chemistry 44, 7849 (2020). http://doi.org/10.1039/D0NJ00987C
Abstract: New zinc naphthalocyanine with bulky 2-naphthyl groups was obtained. Aggregation drastically influences its optical and electrochemical behavior. Spectroelectrochemistry helps to establish the oxidation potential and reveals unusual color change.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 3.3
Times cited: 1
DOI: 10.1039/D0NJ00987C
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“Pd/Lewis acid synergy in macroporous Pd@Na-ZSM-5 for enhancing selective conversion of biomass”. Liu J-W, Wu S-M, Wang L-Y, Tian G, Qin Y, Wu J-X, Zhao X-F, Zhang Y-X, Chang G-G, Wu L, Zhang Y-X, Li Z-F, Guo C-Y, Janiak C, Lenaerts S, Yang X-Y, Chemcatchem , 1 (2020). http://doi.org/10.1002/CCTC.202000868
Abstract: Pd nanometal particles encapsulated in macroporous Na-ZSM-5 with only Lewis acid sites have been successfully synthesized by a steam-thermal approach. The synergistic effect of Pd and Lewis acid sites have been investigated for significant enhancement of the catalytic selectivity towards furfural alcohol in furfural hydroconversion.
Keywords: A1 Journal article; Sustainable Energy, Air and Water Technology (DuEL)
Impact Factor: 4.5
Times cited: 1
DOI: 10.1002/CCTC.202000868
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“Pioneering on single-sludge nitrification/denitrification at 50 °C”. Vandekerckhove TGL, Boon N, Vlaeminck SE, Chemosphere 252, 126527 (2020). http://doi.org/10.1016/J.CHEMOSPHERE.2020.126527
Abstract: Thermophilic nitrification has been proven in lab-scale bioreactors at 50 °C. The challenge is now to develop a solution for thermophilic nitrogen removal, integrating nitrification with denitrification and aerobic carbon removal. This pioneering study aimed at a single-sludge nitrification/denitrification process at 50 °C, through exposing nitrification in a step by step approach to anoxia and/or organics. Firstly, recurrent anoxia was tolerated by a nitrifying community during long-term membrane bioreactor (MBR) operation (85 days), with high ammonium oxidation efficiencies (>98%). Secondly, five organic carbon sources did not affect thermophilic ammonium and nitrite oxidation rates in three-day aerobic batch flask incubations. Moving to long-term tests with sequencing batch reactors (SBR) and MBR (>250 days), good nitrification performance was obtained at increasing COD/Ninfluent ratios (0, 0.5, 1, 2 and 3). Thirdly, combining nitrification, recurrent anoxia and presence of organic carbon resulted in a nitrogen removal efficiency of 92–100%, with a COD/Nremoved of 4.8 ± 0.6 and a nitrogen removal rate of 50 ± 14 mg N g−1 VSS d−1. Overall, this is the first proof of principle thermophilic nitrifiers can cope with redox fluctuations (aerobic/anoxic) and the aerobic or anoxic presence of organic carbon, can functionally co-exist with heterotrophs and that single-sludge nitrification/denitrification can be achieved.
Keywords: A1 Journal article; Engineering sciences. Technology; Sustainable Energy, Air and Water Technology (DuEL)
Impact Factor: 8.8
DOI: 10.1016/J.CHEMOSPHERE.2020.126527
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“Stable single-layers of calcium halides (CaX₂, X = F, Cl, Br, I)”. Baskurt M, Yagmurcukardes M, Peeters FM, Sahin H, Journal Of Chemical Physics 152, 164116 (2020). http://doi.org/10.1063/5.0006011
Abstract: By means of density functional theory based first-principles calculations, the structural, vibrational, and electronic properties of 1H- and 1T-phases of single-layer CaX2 (X = F, Cl, Br, or I) structures are investigated. Our results reveal that both the 1H- and 1T-phases are dynamically stable in terms of their phonon band dispersions with the latter being the energetically favorable phase for all single-layers. In both phases of single-layer CaX2 structures, significant phonon softening occurs as the atomic radius increases. In addition, each structural phase exhibits distinctive Raman active modes that enable one to characterize either the phase or the structure via Raman spectroscopy. The electronic band dispersions of single-layer CaX2 structures reveal that all structures are indirect bandgap insulators with a decrease in bandgaps from fluorite to iodide crystals. Furthermore, the calculated linear elastic constants, in-plane stiffness, and Poisson ratio indicate the ultra-soft nature of CaX2 single-layers, which is quite important for their nanoelastic applications. Overall, our study reveals that with their dynamically stable 1T- and 1H-phases, single-layers of CaX2 crystals can be alternative ultra-thin insulators.
Keywords: A1 Journal article; Condensed Matter Theory (CMT)
Impact Factor: 4.4
Times cited: 14
DOI: 10.1063/5.0006011
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“Towards green ammonia synthesis through plasma-driven nitrogen oxidation and catalytic reduction”. Hollevoet L, Jardali F, Gorbanev Y, Creel J, Bogaerts A, Martens JA, Angewandte Chemie-International Edition (2020). http://doi.org/10.1002/ANIE.202011676
Abstract: Ammonia is an industrial large-volume chemical, with its main application in fertilizer production. It also attracts increasing attention as a green-energy vector. Over the past century, ammonia production has been dominated by the Haber-Bosch process, in which a mixture of nitrogen and hydrogen gas is converted to ammonia at high temperatures and pressures. Haber-Bosch processes with natural gas as the source of hydrogen are responsible for a significant share of the global CO(2)emissions. Processes involving plasma are currently being investigated as an alternative for decentralized ammonia production powered by renewable energy sources. In this work, we present the PNOCRA process (plasma nitrogen oxidation and catalytic reduction to ammonia), combining plasma-assisted nitrogen oxidation and lean NO(x)trap technology, adopted from diesel-engine exhaust gas aftertreatment technology. PNOCRA achieves an energy requirement of 4.6 MJ mol(-1)NH(3), which is more than four times less than the state-of-the-art plasma-enabled ammonia synthesis from N(2)and H(2)with reasonable yield (>1 %).
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 16.6
Times cited: 1
DOI: 10.1002/ANIE.202011676
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“Unlocking the full power of electrochemical fingerprinting for on-site sensing applications”. Moro G, Barich H, Driesen K, Montiel NF, Neven L, Mendonca CD, Thiruvottriyur Shanmugam S, Daems E, De Wael K, Analytical And Bioanalytical Chemistry , 1 (2020). http://doi.org/10.1007/S00216-020-02584-X
Abstract: Electrochemical sensing for the semi-quantitative detection of biomarkers, drugs, environmental contaminants, food additives, etc. shows promising results in point-of-care diagnostics and on-site monitoring. More specifically, electrochemical fingerprint (EF)-based sensing strategies are considered an inviting approach for the on-site detection of low molecular weight molecules. The fast growth of electrochemical sensors requires defining the concept of direct electrochemical fingerprinting in sensing. The EF can be defined as the unique electrochemical signal or pattern, mostly recorded by voltammetric techniques, specific for a certain molecule that can be used for its quantitative or semi-quantitative identification in a given analytical context with specified circumstances. The performance of EF-based sensors can be enhanced by considering multiple features of the signal (i.e., oxidation or reduction patterns), in combination with statistical data analysis or sample pretreatments or by including electrode surface modifiers to enrich the EF. In this manuscript, some examples of EF-based sensors, strategies to improve their performances, and open challenges are discussed to unlock the full power of electrochemical fingerprinting for on-site sensing applications.
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Impact Factor: 4.3
Times cited: 3
DOI: 10.1007/S00216-020-02584-X
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“Modeling the physicochemical properties of natural deep eutectic solvents : a review”. Kovács A, Billen P, Cornet I, Wijnants M, Neyts EC, Chemsuschem 13, 3789 (2020). http://doi.org/10.1002/CSSC.202000286
Abstract: Natural deep eutectic solvents (NADES) are mixtures of naturally derived compounds with a significantly decreased melting point due to the specific interactions among the constituents. NADES have benign properties (low volatility, flammability, toxicity, cost) and tailorable physicochemical properties (by altering the type and molar ratio of constituents), hence they are often considered as a green alternative to common organic solvents. Modeling the relation between their composition and properties is crucial though, both for understanding and predicting their behavior. Several efforts were done to this end, yet this review aims at structuring the present knowledge as an outline for future research. First, we reviewed the key properties of NADES and relate them to their structure based on the available experimental data. Second, we reviewed available modeling methods applicable to NADES. At the molecular level, density functional theory and molecular dynamics allow interpreting density differences and vibrational spectra, and computation of interaction energies. Additionally, properties at the level of the bulk media can be explained and predicted by semi-empirical methods based on ab initio methods (COSMO-RS) and equation of state models (PC-SAFT). Finally, methods based on large datasets are discussed; models based on group contribution methods and machine learning. A combination of bulk media and dataset modeling allows qualitative prediction and interpretation of phase equilibria properties on the one hand, and quantitative prediction of melting point, density, viscosity, surface tension and refractive indices on the other hand. In our view, multiscale modeling, combining the molecular and macroscale methods, will strongly enhance the predictability of NADES properties and their interaction with solutes, yielding truly tailorable solvents to accommodate (bio)chemical reactions.
Keywords: A1 Journal article; Engineering sciences. Technology; Intelligence in PRocesses, Advanced Catalysts and Solvents (iPRACS); Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT); Biochemical Wastewater Valorization & Engineering (BioWaVE)
Impact Factor: 8.4
DOI: 10.1002/CSSC.202000286
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“2,2′-Diaminodiethylamine cellulose powder for trace metal preconcentrations from water”. Reggers C, Van Grieken R, Fresenius' Zeitschrift für analytische Chemie 317, 520 (1984). http://doi.org/10.1007/BF00511918
Abstract: Cellulose powder with 2,2′-diaminodiethylamine (DEN) functional groups exhibits efficient complexation of transition metal cations. Collection yields above 85 % are obtained up to a chelation capacity of 1.5 meq per gram. Since a good collection is obtained for a pH up from 5, no pH adjustments have to be made for natural water samples. The cellulose-DEN powder is insensitive to abundant substances like alkali and alkaline earth ions, and humic matter. Some cations can be eluted efficiently in a small volume of HNO3. Blank concentration levels from the cellulose-DEN powder are reported.
Keywords: A3 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1007/BF00511918
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“Absorption correction for X-ray-fluorescence analysis of aerosol loaded filters”. Adams FC, Van Grieken RE, Analytical chemistry 47, 1767 (1975). http://doi.org/10.1021/AC60361A040
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1021/AC60361A040
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“Absorption correction in electron probe x-ray microanalysis of thin samples”. Markowicz AA, Storms HM, Van Grieken RE, Analytical chemistry 58, 1282 (1986). http://doi.org/10.1021/AC00298A003
Keywords: A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
DOI: 10.1021/AC00298A003
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