| 1. |
- Elhai, M, et al.
(författare)
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Outcomes of patients with systemic sclerosis treated with rituximab in contemporary practice: a prospective cohort study
- 2019
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Ingår i: Annals of the rheumatic diseases. - : BMJ. - 1468-2060 .- 0003-4967. ; 78:7, s. 979-987
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Tidskriftsartikel (refereegranskat)abstract
- To assess the safety and efficacy of rituximab in systemic sclerosis (SSc) in clinical practice.MethodsWe performed a prospective study including patients with SSc from the European Scleroderma Trials and Research (EUSTAR) network treated with rituximab and matched with untreated patients with SSc. The main outcomes measures were adverse events, skin fibrosis improvement, lung fibrosis worsening and steroids use among propensity score-matched patients treated or not with rituximab.Results254 patients were treated with rituximab, in 58% for lung and in 32% for skin involvement. After a median follow-up of 2 years, about 70% of the patients had no side effect. Comparison of treated patients with 9575 propensity-score matched patients showed that patients treated with rituximab were more likely to have skin fibrosis improvement (22.7 vs 14.03 events per 100 person-years; OR: 2.79 [1.47–5.32]; p=0.002). Treated patients did not have significantly different rates of decrease in forced vital capacity (FVC)>10% (OR: 1.03 [0.55–1.94]; p=0.93) nor in carbon monoxide diffusing capacity (DLCO) decrease. Patients having received rituximab were more prone to stop or decrease steroids (OR: 2.34 [1.56–3.53], p<0.0001). Patients treated concomitantly with mycophenolate mofetil had a trend for better outcomes as compared with patients receiving rituximab alone (delta FVC: 5.22 [0.83–9.62]; p=0.019 as compared with controls vs 3 [0.66–5.35]; p=0.012).ConclusionRituximab use was associated with a good safety profile in this large SSc-cohort. Significant change was observed on skin fibrosis, but not on lung. However, the limitation is the observational design. The potential stabilisation of lung fibrosis by rituximab has to be addressed by a randomised trial.
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| 2. |
- Ritopecki, Milica S. S., et al.
(författare)
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The Local Coordination Effects on the Reactivity and Speciation of Active Sites in Graphene-Embedded Single-Atom Catalysts over Wide pH and Potential Range
- 2022
-
Ingår i: Nanomaterials. - : MDPI AG. - 2079-4991. ; 12:23
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the catalytic performance of different materials is of crucial importance for achieving further technological advancements. This especially relates to the behaviors of different classes of catalysts under operating conditions. Here, we analyzed the effects of local coordination of metal centers (Mn, Fe, Co) in graphene-embedded single-atom catalysts (SACs). We started with well-known M@N-4-graphene catalysts and systematically replaced nitrogen atoms with oxygen or sulfur atoms to obtain M@OxNy-graphene and M@SxNy-graphene SACs (x + y = 4). We show that local coordination strongly affects the electronic structure and reactivity towards hydrogen and oxygen species. However, stability is even more affected. Using the concept of Pourbaix plots, we show that the replacement of nitrogen atoms in metal coordinating centers with O or S destabilized the SACs towards dissolution, while the metal centers were easily covered by O and OH, acting as additional ligands at high anodic potentials and high pH values. Thus, not only should local coordination be considered in terms of the activity of SACs, but it is also necessary to consider its effects on the speciation of SAC active centers under different potentials and pH conditions.
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| 3. |
- Milikić, J., et al.
(författare)
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A Pt/MnV2O6 nanocomposite for the borohydride oxidation reaction
- 2021
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Ingår i: Journal of Energy Challenges and Mechanics. - : Elsevier B.V.. - 2056-9386. ; 55, s. 428-436
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Tidskriftsartikel (refereegranskat)abstract
- Problems associated with carbon support corrosion under operating fuel cell conditions require the identification of alternative supports for platinum-based nanosized electrocatalysts. Platinum supported on manganese vanadate (Pt/MnV2O6) was prepared by microwave irradiation method and characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy with energy dispersive spectroscopy, and transmission electron microscopy. The borohydride oxidation reaction (BOR) on Pt/MnV2O6 was studied in highly alkaline media using voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. BOR electrocatalytic activity of Pt/MnV2O6 was also compared with that of commercial Pt/C (46 wt% Pt) electrocatalyst. The apparent activation energy of BOR at Pt/MnV2O6 was estimated to be 32 kJ mol−1 and the order of reaction to be 0.51, indicating that borohydride hydrolysis proceeds in parallel with its oxidation. Long-term stability of Pt/MnV2O6 under BOR typical conditions was observed. A laboratory-scale direct borohydride fuel cell assembled with a Pt/MnV2O6 anode reached a specific power of 274 W g−1. Experimental results on Pt/MnV2O6 were complemented by DFT calculations, which indicated good adherence of Pt to MnV2O6, beneficial for electrocatalyst stability.
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| 4. |
- Jovanović, A., et al.
(författare)
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Structural and electronic properties of V2O5 and their tuning by doping with 3d elements-modelling using the DFT+ U method and dispersion correction
- 2018
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 20:20, s. 13934-13943
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Tidskriftsartikel (refereegranskat)abstract
- New electrode materials for alkaline-ion batteries are a timely topic. Among many promising candidates, V2O5 is one of the most interesting cathode materials. While having very high theoretical capacity, in practice, its performance is hindered by its low stability and poor conductivity. As regards the theoretical descriptions of V2O5, common DFT-GGA calculations fail to reproduce both the electronic and crystal structures. While the band gap is underestimated, the interlayer spacing is overestimated as weak dispersion interactions are not properly described within GGA. Here we show that the combination of the DFT+U method and semi-empirical D2 correction can compensate for the drawbacks of the GGA when it comes to the modelling of V2O5. When compared to common PBE calculations, with a modest increase in the computational cost, PBE+U+D2 fully reproduced the experimental band gap of V2O5, while the errors in the lattice parameters are only a few percent. Using the proposed PBE+U+D2 methodology we studied the doping of V2O5 with 3d elements (from Sc to Zn). We show that both the structural and electronic parameters are affected by doping. Most importantly, a significant increase in conductivity is expected upon doping, which is of great importance for the application of V2O5 in metal-ion batteries.
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| 5. |
- Ritopečki, Milica S., et al.
(författare)
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Density Functional Theory Analysis of the Impact of Boron Concentration and Surface Oxidation in Boron-Doped Graphene for Sodium and Aluminum Storage
- 2023
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Ingår i: C - Journal of Carbon Research. - : MDPI. - 2311-5629. ; 9:4
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Tidskriftsartikel (refereegranskat)abstract
- Graphene is thought to be a promising material for many applications. However, pristine graphene is not suitable for most electrochemical devices, where defect engineering is crucial for its performance. We demonstrate how the boron doping of graphene can alter its reactivity, electrical conductivity and potential application for sodium and aluminum storage, with an emphasis on novel metal-ion batteries. Using Density Functional Theory calculations, we investigate both the influence of boron concentration and the oxidation of the material on the mentioned properties. It is demonstrated that the presence of boron in graphene increases its reactivity towards atomic hydrogen and oxygen-containing species; in other words, it makes B-doped graphene more prone to oxidation. Additionally, the presence of these surface functional groups significantly alters the type and strength of the interaction of Na and Al with the given materials. Boron-doping and the oxidation of graphene is found to increase the Na storage capacity of graphene by a factor of up to four, and the calculated sodiation potentials indicate the possibility of using these materials as electrode materials in high-voltage Na-ion batteries.
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| 6. |
- Cha, Gihoon, et al.
(författare)
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As a single atom Pd outperforms Pt as the most active co-catalyst for photocatalytic H-2 evolution
- 2021
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Ingår i: ISCIENCE. - : Elsevier BV. - 2589-0042. ; 24:8
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Tidskriftsartikel (refereegranskat)abstract
- Here, we evaluate three different noble metal co-catalysts (Pd, Pt, and Au) that are present as single atoms (SAs) on the classic benchmark photocatalyst, TiO2. To trap the single atoms on the surface, we introduced controlled surface vacancies (Ti3+-Ov) on anatase TiO2 nanosheets by a thermal reduction treatment. After anchoring identical loadings of single atoms of Pd, Pt, and Au, we measure the photocatalytic H-2 generation rate and compare it to the classic nanoparticle co-catalysts on the nanosheets. While nanoparticles yield the well-established the hydrogen evolution reaction activity sequence (Pt > Pd > Au), for the single atom form, Pd radically outperforms Pt and Au. Based on density functional theory (DFT), we ascribe this unusual photocatalytic co-catalyst sequence to the nature of the charge localization on the noble metal SAs embedded in the TiO2 surface.
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| 7. |
- Dobrota, Ana S., et al.
(författare)
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A DFT study of the interplay between dopants and oxygen functional groups over the graphene basal plane - implications in energy-related applications
- 2017
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : ROYAL SOC CHEMISTRY. - 1463-9076 .- 1463-9084. ; 19:12, s. 8530-8540
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Tidskriftsartikel (refereegranskat)abstract
- Understanding the ways graphene can be functionalized is of great importance for many contemporary technologies. Using density functional theory calculations we investigate how vacancy formation and substitutional doping by B, N, P and S affect the oxidizability and reactivity of the graphene basal plane. We find that the presence of these defects enhances the reactivity of graphene. In particular, these sites act as strong attractors for OH groups, suggesting that the oxidation of graphene could start at these sites or that these sites are the most difficult to reduce. Scaling between the OH and H adsorption energies is found on both reduced and oxidized doped graphene surfaces. Using the O-2 molecule as a probe we show that a proper modelling of doped graphene materials has to take into account the presence of oxygen functional groups.
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| 8. |
- Dobrota, Ana S., et al.
(författare)
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A general view on the reactivity of the oxygen-functionalized graphene basal plane
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 18:9, s. 6580-6586
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Tidskriftsartikel (refereegranskat)abstract
- In this contribution we inspect the adsorption of H, OH, Cl and Pt on oxidized graphene using DFT calculations. The introduction of epoxy and hydroxyl groups on the graphene basal plane significantly alters its chemisorption properties, which can be attributed to the deformation of the basal plane and the type and distribution of these groups. We show that a general scaling relation exists between the hydrogen binding energies and the binding energies of other investigated adsorbates, which allows for a simple probing of the reactivity of oxidized graphene with only one adsorbate. The electronic states of carbon atoms located within the 2 eV interval below the Fermi level are found to be responsible for the interaction of the basal plane with the chosen adsorbates. The number of electronic states situated in this energy interval is shown to correlate with hydrogen binding energies.
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| 9. |
- Dobrota, Ana S., et al.
(författare)
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Altering the reactivity of pristine, N- and P-doped graphene by strain engineering : A DFT view on energy related aspects
- 2020
-
Ingår i: Applied Surface Science. - : ELSEVIER. - 0169-4332 .- 1873-5584. ; 514
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Tidskriftsartikel (refereegranskat)abstract
- For carbon-based materials, in contrast to metal surfaces, a general relationship between strain and reactivity is not yet established, even though there are literature reports on strained graphene. Knowledge of such relationships would be extremely beneficial for understanding the reactivity of graphene-based surfaces and finding optimisation strategies which would make these materials more suitable for targeted applications. Here we investigate the effects of compressive and tensile strain (up to +/- 5%) on the structure, electronic properties and reactivity of pure, N-doped and P-doped graphene, using DFT calculations. We demonstrate the possibility of tuning the topology of the graphene surface by strain, as well as by the choice of the dopant atom. The reactivity of (doped) strained graphene is probed using H and Na as simple adsorbates of great practical importance. Strain can both enhance and weaken H and Na adsorption on (doped) graphene. In case of Na adsorption, a linear relationship is observed between the Na adsorption energy on P-doped graphene and the phosphorus charge. A linear relationship between the Na adsorption energy on flat graphene surfaces and strain is found. Based on the adsorption energies and electrical conductivity, potentially good candidates for hydrogen storage and sodiumion battery electrodes are discussed.
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| 10. |
- Dobrota, Ana S., et al.
(författare)
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Functionalized graphene for sodium battery applications : the DFT insights
- 2017
-
Ingår i: Electrochimica Acta. - : Elsevier. - 0013-4686 .- 1873-3859. ; 250, s. 185-195
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Tidskriftsartikel (refereegranskat)abstract
- Considering the increasing interest in the use of graphene-based materials for energy conversion and storage applications, we have performed a DFT study of Na interaction with doped graphene, both in non-oxidized and oxidized forms. Oxidation seems to play the crucial role when it comes to the interaction of doped graphene materials with sodium. The dopants act as attractors of OH groups, making the material prone to oxidation, and therefore altering its affinity towards Na. In some cases, this can result in hydroxide or water formation - an irreversible change lethal for battery performance. Our results suggest that one should carefully control the oxidation level of doped graphene-based materials if they are to be used as sodium battery electrode materials as the optimal oxidation level depends on the dopant type.
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| 11. |
- Dobrota, Ana S., et al.
(författare)
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Oxidized graphene as an electrode material for rechargeable metal-ion batteries - a DFT point of view
- 2015
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Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686 .- 1873-3859. ; 176, s. 1092-1099
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Tidskriftsartikel (refereegranskat)abstract
- In line with a growing interest in the use of graphene-based materials for energy storage applications and active research in the field of rechargeable metal-ion batteries we have performed a DFT based computational study of alkali metal atoms (Li, Na and K) interaction with an oxidized graphene. The presence of oxygen surface groups (epoxy and hydroxyl) alters the chemisorption properties of graphene. In particular, we observe that the epoxy groups are redox active and enhance the alkali metal adsorption energies by a factor of 2 or more. When an alkali metal atom interacts with hydroxyl-graphene the formation of metal-hydroxide is observed. In addition to a potential boost of metal ion storage capability, oxygen functional groups also prevent the precipitation of the metal phase. By simulating lithiation/de-lithiation process on epoxy-graphenes, it was concluded that the oxidized graphene can undergo structural changes during battery operation. Our results suggest that the content and the type of oxygen surface groups should be carefully tailored to maximize the performance of metal-ion batteries. This is mainly related to the control of the oxidation level in order to provide enough active centers for metal ion storage while preserving sufficient electrical conductivity.
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| 12. |
- Dobrota, Ana S., et al.
(författare)
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Stabilization of alkali metal ions interaction with OH-functionalized graphene via clustering of OH groups - implications in charge storage applications
- 2016
-
Ingår i: RSC Advances. - : Royal Society of Chemistry (RSC). - 2046-2069. ; 6:63, s. 57910-57919
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Tidskriftsartikel (refereegranskat)abstract
- Graphene synthesized by reduction of graphene oxide, depending on the degree of reduction, retains a certain amount of surface OH groups. Considering the surface OH groups/graphene layer system by means of density functional theory calculations, we evidenced the tendency of OH groups to cluster, resulting in enhanced system stability and no band gap opening. In the oxygen concentration range between 1.8 and 8.47 at%, with the addition of each new OH group, integral binding energy decreases, while differential binding energy shows the boost at even numbers of OH groups. Furthermore, we found that the clustering of OH groups over graphene basal plane plays a crucial role in enhancing the interactions with alkali metals. Namely, if alkali metal atoms interact with individual OH groups only, the interaction leads to an irreversible formation of MOH phase. When alkali atoms interact with clusters containing odd number of OH groups, a reversible transfer of an electron charge from the metal atom to the substrate takes place without OH removal. The strength of the interaction in general increases from Li to K. In an experimental investigation of a graphene sample which dominantly contains OH groups, we have shown that the trend in the specific interaction strength reflects to gravimetric capacitances measured in alkali metal chloride solutions. We propose that the charge stored in OH groups which interact with alkali metal cation and the pi electronic system of the graphene basal plane presents the main part of its pseudocapacitance.
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| 13. |
- Gebremariam, Goitom K., et al.
(författare)
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Hydrogen Evolution Volcano(es)-From Acidic to Neutral and Alkaline Solutions
- 2022
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Ingår i: Catalysts. - : MDPI AG. - 2073-4344. ; 12:12
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Tidskriftsartikel (refereegranskat)abstract
- As the global energy crisis continues, efficient hydrogen production is one of the hottest topics these days. In this sense, establishing catalytic trends for hydrogen production is essential for choosing proper H-2 generation technology and catalytic material. Volcano plots for hydrogen evolution in acidic media are well-known, while a volcano plot in alkaline media was constructed ten years ago using theoretically calculated hydrogen binding energies. Here, for the first time, we show that the volcano-type relationships are largely maintained in a wide range of pH values, from acidic to neutral and alkaline solutions. We do this using theoretically calculated hydrogen binding energies on clean metallic surfaces and experimentally measured hydrogen evolution overpotentials. When metallic surfaces are exposed to high anodic potentials, hydrogen evolution can be boosted or significantly impeded, depending on the type of metal and the electrolyte in which the reaction occurs. Such effects are discussed here and can be used to properly tailor catalytic materials for hydrogen production via different water electrolysis technologies.
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| 14. |
- Gutic, Sanjin J., et al.
(författare)
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Improved catalysts for hydrogen evolution reaction in alkaline solutions through the electrochemical formation of nickel-reduced graphene oxide interface
- 2017
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : ROYAL SOC CHEMISTRY. - 1463-9076 .- 1463-9084. ; 19:20, s. 13281-13293
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Tidskriftsartikel (refereegranskat)abstract
- H-2 production via water electrolysis plays an important role in hydrogen economy. Hence, novel cheap electrocatalysts for the hydrogen evolution reaction ( HER) are constantly needed. Here, we describe a simple method for the preparation of composite catalysts for H-2 evolution, consisting in simultaneous reduction of the graphene oxide film, and electrochemical deposition of Ni on its surface. The obtained composites (Ni@rGO), compared to pure electrodeposited Ni, show an improved electrocatalytic activity towards HER in alkaline media. We found that the activity of the Ni@rGO catalysts depends on the surface composition ( Ni vs. C mole ratio) and on the level of structural disorder of the rGO support. We suggest that HER activity is improved via H-ads spillover from the Ni particles to the rGO support, where quick recombination to molecular hydrogen is favored. A deeper insight into such a mechanism of H-2 production was achieved by kinetic Monte-Carlo simulations. These simulations enabled the reproduction of experimentally observed trends under the assumption that the support can act as a Hads acceptor. We expect that the proposed procedure for the production of novel HER catalysts could be generalized and lead to the development of a new generation of HER catalysts by tailoring the catalyst/support interface.
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| 15. |
- Jovanović, Aleksandar Z., et al.
(författare)
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Reactivity of Stone-Wales defect in graphene lattice – DFT study
- 2023
-
Ingår i: FlatChem. - : Elsevier. - 2452-2627. ; 42
-
Tidskriftsartikel (refereegranskat)abstract
- Understanding the reactivity of carbon surfaces is crucial for the development of advanced functional materials. The SW defect is commonly present in carbon materials, but a comprehensive understanding of its effects on the reactivity of carbons is missing. In this study, we systematically investigate the reactivity of graphene surfaces with the Stone-Wales (SW) defect using Density Functional Theory calculations. We explore the atomic adsorption of various elements, including rows 1–3 of the Periodic Table, potassium, calcium, and selected transition metals. Our results demonstrate that the SW defect enhances binding with the studied adsorbates when compared to pristine graphene, with carbon and silicon showing the most significant differences. Additionally, we examine the effects of mechanical deformation on the lattice by constraining the system with the SW defect to the pristine graphene cell. Interestingly, these constraints lead to even stronger binding interactions. Furthermore, for carbon, nitrogen, and oxygen adsorbates, we observe that mechanical deformation triggers the incorporation of adatoms into the carbon bond network, leading to the reorganization of the SW defect structure. This work establishes a foundation for future studies in the defect and strain engineering of graphene, opening avenues for developing advanced materials and catalysts with enhanced reactivity and performance.
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| 16. |
- Karacic, Dalibor, et al.
(författare)
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When supporting electrolyte matters - Tuning capacitive response of graphene oxide via electrochemical reduction in alkali and alkaline earth metal chlorides
- 2019
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Ingår i: Electrochimica Acta. - : Elsevier. - 0013-4686 .- 1873-3859. ; 297, s. 112-117
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Tidskriftsartikel (refereegranskat)abstract
- The ability to tune charge storage properties of graphene oxide ( GO) is of utmost importance for energy conversion applications. Here we show that the electrochemical reduction of GO is highly sensitive to the cations present in the solution. GO is reduced at more negative potential in alkali metal chloride solutions than in alkaline earth metal chlorides. During the reduction, the capacitance of GO increases from 10 to 70 times. The maximum capacitances of reduced GO are between 65 and 130 F g(-1), depending on the electrolyte and the presence of conductive additive. We propose that different interactions of cations with oxygen functional groups of GO during the reduction are responsible for the observed effect. This hypothesis has been confirmed by Density Functional Theory calculations of alkali and alkaline earth metals interactions with epoxy-functionalized graphene sheet.
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| 17. |
- Krstajić Pajić, Mila N., et al.
(författare)
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Activation of Osmium by the Surface Effects of Hydrogenated TiO2 Nanotube Arrays for Enhanced Hydrogen Evolution Reaction Performance
- 2023
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society. - 1944-8244 .- 1944-8252. ; 15:26, s. 31459-31469
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Tidskriftsartikel (refereegranskat)abstract
- Efficient cathodes for the hydrogen evolution reaction (HER) in acidic water electrolysis rely on the use of expensive platinum group metals (PGMs). However, to achieve economically viable operation, both the content of PGMs must be reduced and their intrinsically strong H adsorption mitigated. Herein, we show that the surface effects of hydrogenated TiO2 nanotube (TNT) arrays can make osmium, a so far less-explored PGM, a highly active HER electrocatalyst. These defect-rich TiO2 nanostructures provide an interactive scaffold for the galvanic deposition of Os particles with modulated adsorption properties. Through systematic investigations, we identify the synthesis conditions (OsCl3 concentration/temperature/reaction time) that yield a progressive improvement in Os deposition rate and mass loading, thereby decreasing the HER overpotential. At the same time, the Os particles deposited by this procedure remain mainly sub-nanometric and entirely cover the inner tube walls. An optimally balanced Os@TNT composite prepared at 3 mM/55 °C/30 min exhibits a record low overpotential (η) of 61 mV at a current density of 100 mA cm-2, a high mass activity of 20.8 A mgOs-1 at 80 mV, and a stable performance in an acidic medium. Density functional theory calculations indicate the existence of strong interactions between the hydrogenated TiO2 surface and small Os clusters, which may weaken the Os-H* binding strength and thus boost the intrinsic HER activity of Os centers. The results presented in this study offer new directions for the fabrication of cost-effective PGM-based catalysts and a better understanding of the synergistic electronic interactions at the PGM|TiO2 interface.
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| 18. |
- Novcic, Katarina A., et al.
(författare)
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Theoretical analysis of doped graphene as cathode catalyst in Li-O-2 and Na-O-2 batteries - the impact of the computational scheme
- 2020
-
Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686 .- 1873-3859. ; 354
-
Tidskriftsartikel (refereegranskat)abstract
- Understanding the reactions in M-O-2 cells (M = Li or Na) is of great importance for further advancement of this promising technology. Computational modelling can be helpful along this way, but an adequate approach is needed to model such complex systems. We propose a new scheme for modelling processes in M-O-2 cells, where reference energies are obtained from high-level theory, CCSD(T), while the interactions of reaction intermediates with catalyst surfaces are extracted from computationally less expensive DFT. The approach is demonstrated for the case of graphene-based surfaces as model catalysts in Li-O-2 and Na-O-2 cells using the minimum viable mechanism. B-doped graphene was identified as the best catalyst amongst considered surfaces, while pristine graphene performs poorly. Moreover, we show that the inclusion of dispersion corrections for DFT has a significant impact on calculated discharge and charge potentials and suggests that long-range dispersion interactions should always be considered when graphene-based materials are modelled as electrocatalysts. Finally, we offer general guidelines for designing new ORR catalysts for M-O-2 cells in terms of the optimization of the interactions of catalyst surface with reaction intermediates.
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| 19. |
- Pasti, Igor A., et al.
(författare)
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Atomic adsorption on graphene with a single vacancy : systematic DFT study through the periodic table of elements
- 2018
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 20:2, s. 858-865
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Tidskriftsartikel (refereegranskat)abstract
- Vacancies in graphene present sites of altered chemical reactivity and open possibilities to tune graphene properties by defect engineering. The understanding of chemical reactivity of such defects is essential for successful implementation of carbon materials in advanced technologies. We report the results of a systematic DFT study of atomic adsorption on graphene with a single vacancy for the elements of rows 1-6 of the periodic table of elements (PTE), excluding lanthanides. The calculations have been performed using the PBE, long-range dispersion interaction-corrected PBE (PBE+D2 and PBE+D3) and non-local vdW-DF2 functionals. We find that most elements strongly bind to the vacancy, except for the elements of groups 11 and 12, and noble gases, for which the contribution of dispersion interaction to bonding is most significant. The strength of the interaction with the vacancy correlates with the cohesive energy of the elements in their stable phases: the higher the cohesive energy is, the stronger bonding to the vacancy can be expected. As most atoms can be trapped at the SV site we have calculated the potentials of dissolution and found that in most cases the metals adsorbed at the vacancy are more "noble" than they are in their corresponding stable phases.
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| 20. |
- Pasti, Igor A., et al.
(författare)
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Atomic adsorption on pristine graphene along the Periodic Table of Elements - From PBE to non-local functionals
- 2018
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Ingår i: Applied Surface Science. - : ELSEVIER SCIENCE BV. - 0169-4332 .- 1873-5584. ; 436, s. 433-440
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Tidskriftsartikel (refereegranskat)abstract
- The understanding of atomic adsorption on graphene is of high importance for many advanced technologies. Here we present a complete database of the atomic adsorption energies for the elements of the Periodic Table up to the atomic number 86 (excluding lanthanides) on pristine graphene. The energies have been calculated using the projector augmented wave (PAW) method with PBE, long-range dispersion interaction corrected PBE (PBE+D2, PBE+D3) as well as non-local vdW-DF2 approach. The inclusion of dispersion interactions leads to an exothermic adsorption for all the investigated elements. Dispersion interactions are found to be of particular importance for the adsorption of low atomic weight earth alkaline metals, coinage and s-metals (11th and 12th groups), high atomic weight p-elements and noble gases. We discuss the observed adsorption trends along the groups and rows of the Periodic Table as well some computational aspects of modelling atomic adsorption on graphene.
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