Surface-dependent properties and morphological transformations of rutile GeO2 nanoparticles
Source abstract
Abstract
Recently, the knowledge of surface-dependent properties has attracted a lot of attention since it is crucial for materials functionalization based on the morphological control of nanoparticles (NPs). This study describes the surface-dependent properties and morphological transformation routes of rutile germanium dioxide (r-GeO2) using the density functional theory (DFT) and the Wulff construction procedure. The calculations revealed the following order of relative surface stability: (1 1 0) > (1 0 0) > (3 2 1) > (3 1 1) > (2 0 1) > (2 1 1) > (1 0 1) > (1 0 3) > (0 0 1) > (1 1 1), with the Ge-O bonds being attributed to Ge4p-O2p and Ge4s-O2p interactions. The results demonstrate that the different coordination breakages on the outermost polyhedra are related to atomic charges, band gap, relative stability, and Fermi energy. Additionally, a map of the morphological transformation routes and the band alignment were elaborated, showing that cubic, octahedral, or hexadecahedral morphologies can have photocatalytic activity for H2 production via water splitting. The methodology and results reported herein can help target the synthesis and functionalization of rutile-type materials.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Advanced Photocatalysis Techniques · Ga2O3 and related materials · Quantum Dots Synthesis And Properties
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (55)
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1. L. Nagarajan, R.A. de Souza, D. Samuelis, I. Valov, A. Börger, J. Janek, K.D. Becker, P.C. Schmidt, M. Martin, A chemically driven insulator–metal transition in non-stoichiometric and amorphous gallium oxide, Nature Materials 2008 7:5. 7 (2008) 391–398. 10.1038/nmat2164.10.1038/nmat2164 ↗
2. J. Kim, T. Sekiya, N. Miyokawa, N. Watanabe, K. Kimoto, K. Ide, Y. Toda, S. Ueda, N. Ohashi, H. Hiramatsu, H. Hosono, T. Kamiya, Conversion of an ultra-wide bandgap amorphous oxide insulator to a semiconductor, NPG Asia Materials 2017 9:3. 9 (2017) e359–e359. 10.1038/am.2017.20.10.1038/am.2017.20 ↗
3. E. Chikoidze, D.J. Rogers, F.H. Teherani, C. Rubio, G. Sauthier, H.J. von Bardeleben, T. Tchelidze, C. Ton-That, A. Fellous, P. Bove, E. v. Sandana, Y. Dumont, A. Perez-Tomas, Puzzling robust 2D metallic conductivity in undoped β-Ga2O3 thin films, Materials Today Physics. 8 (2019) 10–17. 10.1016/J.MTPHYS.2018.11.006.10.1016/j.mtphys.2018.11.006 ↗
4. Comparison between The ultra-wide band gap semiconductor AlGaN and GaN10.1088/1757-899X/738/1/012009 ↗
5. P-Type Ultrawide-Band-Gap Spinel ZnGa2O4: new perspectives for energy electronics10.1021/acs.cgd.9b01669 ↗
6. Fast X-ray detectors based on bulk β-Ga2O3 (Fe)10.1007/s10853-020-04665-9 ↗
7. C. v. Ramana, G. Carbajal-Franco, R.S. Vemuri, I.B. Troitskaia, S.A. Gromilov, V. v. Atuchin, Optical properties and thermal stability of germanium oxide (GeO2) nanocrystals with α-quartz structure, Materials Science and Engineering: B. 174 (2010) 279–284. 10.1016/J.MSEB.2010.03.060.10.1016/j.mseb.2010.03.060 ↗
8. Quasiparticle band structure and optical properties of rutile GeO2, an ultra-wide-band-gap semiconductor10.1063/1.5111318 ↗
9. Ultrawide bandgap semiconductors10.1063/5.0055292 ↗
10. Toward the predictive discovery of ambipolarly dopable ultra-wide-band-gap semiconductors: the case of rutile GeO210.1063/5.0056674 ↗
11. Establishment of a growth route of crystallized rutile GeO2 thin film (≧1 μm/h) and its structural properties10.1063/5.0060785 ↗
12. Thermal conductivity of rutile germanium dioxide10.1063/5.0011358 ↗
13. Electron and hole mobility of rutile GeO2 from first principles: an ultrawide-bandgap semiconductor for power electronics10.1063/5.0033284 ↗
14. Facile synthesis of new polyhedron-like WO 3 /butterfly-like Ag 2 MoO 4 p–n junction photocatalysts with higher photocatalytic activity in UV/solar region light10.1039/C9NJ05801J ↗
15. An excellent Z-scheme Ag2MoO4/Bi4Ti3O12 heterojunction photocatalyst: construction strategy and application in environmental purification10.1016/j.apt.2021.01.039 ↗
16. d10 or d0? Theoretical and experimental comparison between rutile GeO2 and TiO2 for photocatalytic water splitting10.1039/D0CC06883G ↗
17. Bulk and surface DFT investigations of the electronic and magnetic properties of CsXNO (X = Mg, Ca and Sr) quaternary Heusler alloys10.1016/j.matchemphys.2020.122923 ↗
18. The subsurface diffusion of hydrogen on rutile TiO2 Surfaces: a Periodic DFT Study10.1007/s11244-021-01518-w ↗
19. CH4 dissociation and CC coupling on Mo-terminated MoC surfaces: a DFT study10.1016/j.cattod.2019.03.020 ↗
20. In silico investigations of alginate biopolymer on the Fe (110), Cu (111), Al (111) and Sn (001) surfaces in acidic media: quantum chemical and molecular mechanic calculations10.1016/j.molliq.2020.113479 ↗
21. Frage der Geschwindigkeit des Wachsthums und der Auflösung der Krystallflächen10.1524/zkri.1901.34.1.449 ↗
22. Propriedades estruturais e eletrônicas de nanofilmes de TiO2 anatase: cálculos B3LYP-D* em sistemas periódicos bidimensionais
23. Connecting morphology and photoluminescence emissions in β-Ag2MoO4 microcrystals10.1016/j.ceramint.2021.10.156 ↗
24. L.H. da S. Lacerda, M.A. San-Miguel, DFT approaches unraveling the surface and morphological properties of MnMoO4, Appl Surf Sci. 567 (2021) 150882. 10.1016/J.APSUSC.2021.150882.10.1016/j.apsusc.2021.150882 ↗
25. Revisiting the identity of δ-MgCl2: Part II. Morphology and exposed surfaces studied by vibrational spectroscopies and DFT calculation10.1016/j.jcat.2020.04.017 ↗
26. DFT investigations into surface stability and morphology of δ-MoC catalyst10.1016/j.apsusc.2019.143790 ↗
27. Morphology of MoP catalyst under hydrogenation conditions: a DFT based thermodynamics study, Molecular
28. A. Abbaspour Tamijani, E. Ebrahimiaqda, Anomalous behavior of rutile GeO2 facets: A computational study, Mater Chem Phys. 199 (2017) 552–556. 10.1016/J.MATCHEMPHYS.2017.07.027.10.1016/j.matchemphys.2017.07.027 ↗
29. Rutile (β-)MnO2 surfaces and vacancy formation for high electrochemical and catalytic performance10.1021/ja4092962 ↗
30. Computational simulations of morphological transformations by surface structures: the case of rutile TiO2 phase10.1590/1980-5373-mr-2016-0709 ↗
31. First-principles atomistic Wulff constructions for an equilibrium rutile TiO2 shape modeling10.1016/j.apsusc.2017.12.050 ↗
32. Density functional theory study of rutile VO2 surfaces10.1063/1.4758319 ↗
33. Density functional theory study on the structural and electronic properties of low index rutile surfaces for TiO2/SnO2/TiO 2 and SnO2/TiO2/SnO2 composite systems10.1021/jp801604n ↗
34. Quantum-mechanical condensed matter simulations with CRYSTAL10.1002/wcms.1360 ↗
35. A.D. Becke, Density‐functional thermochemistry. IV. A new dynamical correlation functional and implications for exact‐exchange mixing, J Chem Phys. 104 (1998) 1040. 10.1063/1.470829.10.1063/1.470829 ↗
36. Semiempirical GGA-type density functional constructed with a long-range dispersion correction10.1002/jcc.20495 ↗
37. P.B.C.S.M.R.R.D. G Sophia, Systematic influence of atomic substitution on the phase diagram of ABO3 ferroelectric perovskites, (2014).
38. Beryllium oxide nanotubes and their connection to the flat monolayer10.1021/jp402340z ↗
39. E.O. Gomes, G.S.L. Fabris, M.M. Ferrer, F. v. Motta, M.R.D. Bomio, J. Andres, E. Longo, J.R. Sambrano, Computational procedure to an accurate DFT simulation to solid state systems, Comput Mater Sci. 170 (2019) 109176. 10.1016/j.commatsci.2019.109176.10.1016/j.commatsci.2019.109176 ↗
40. W.H. Baur, A.A. Khan, IUCr, Rutile-type compounds. IV. SiO2, GeO2 and a comparison with other rutile-type structures, Urn:Issn:0567-7408. 27 (1971) 2133–2139. 10.1107/S0567740871005466.10.1107/S0567740871005466 ↗
41. Rutile GeO2: an ultrawide-band-gap semiconductor with ambipolar doping10.1063/1.5088370 ↗
42. Extending Hirshfeld-I to bulk and periodic materials10.1002/jcc.23088 ↗
43. Bulk moduli and high-pressure crystal structures of rutile-type compounds10.1016/0022-3697(81)90074-3 ↗
44. Structural Studies of Rutile-Type Metal Dioxides
45. Exciton structure in the u.v.-absorption edge of tetragonal GeO210.1016/0038-1098(78)90311-3 ↗
46. K. Robinson, G. v. Gibbs, P.H. Ribbe, Quadratic Elongation: A Quantitative Measure of Distortion in Coordination Polyhedra, Science (1979). 172 (1971) 567–570. 10.1126/SCIENCE.172.3983.567.10.1126/science.172.3983.567 ↗
47. A new route to charge distributions in ionic solids10.1016/0022-5088(89)90411-6 ↗
48. Heteroepitaxy of (1 0 0)-oriented rutile GeO2 film on c-plane sapphire by pulsed laser deposition10.1016/j.matlet.2022.132945 ↗
49. Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets10.1021/jp202489s ↗
50. VESTA: a three-dimensional visualization system for electronic and structural analysis
51. Morphological Transformation Network of Nanoparticles via DFT Simulations10.1021/acs.cgd.0c00423 ↗
52. J.A.S. Laranjeira, G.S.L. Fabris, A.R. Albuquerque, M.M. Ferrer, J.R. Sambrano, Morphological transformations mapping of CaXO4 (X = Mo or W) and their surface stability, Mater Today Commun. (2022) 104178. 10.1016/J.MTCOMM.2022.104178.10.1016/j.mtcomm.2022.104178 ↗
53. Growth mechanism and growth habit of oxide crystals10.1016/S0022-0248(99)00076-7 ↗
54. Morphology and crystal phase evolution of GeO2 in liquid phase deposition process10.1016/j.jcrysgro.2011.11.024 ↗
55. First principles scheme to evaluate band edge positions in potential transition metal oxide photocatalysts and photoelectrodes10.1039/c1cp22128k ↗