Revealing the effect of Co/Cu (d7/d9) cationic doping on an electronic acceptor ZnO nanocage surface for the adsorption of citric acid, vinyl alcohol, and sulfamethoxazole ligands: DFT-D3, QTAIM, IGM-NCI, and MD analysis

被引：5

作者：

Gassoumi, B. ^{[1
]}

Mahmoud, A. M. Ahmed ^{[2
]}

Nasr, S. ^{[3
,4
]}

Karayel, A. ^{[5
]}

Ozkinali, S. ^{[6
]}

Castro, M. E. ^{[7
]}

Melendez, F. J. ^{[8
]}

Mahdouani, M. ^{[2
]}

Nouar, L. ^{[9
]}

Madi, F. ^{[9
]}

Ghalla, H. ^{[10
]}

Bourguiga, R. ^{[2
]}

Ben Chaabane, R. ^{[1
]}

Zhou, Y. ^{[11
]}

机构：

[1] Univ Monastir, Fac Sci Monastir, Lab Adv Mat & Interfaces LIMA, Ave Environm, Monastir 5000, Tunisia

[2] Univ Carthage, Fac Sci Bizerte, Mat Phys Lab Struct & Properties, Grp Phys Nanometr Components & Devices, Bizerte 7021, Tunisia

[3] King Khalid Univ, Res Ctr Adv Mat Sci RCAMS, POB 9004, Abha 61413, Saudi Arabia

[4] King Khalid Univ, Fac Sci, Dept Chem, POB 9004, Abha 61413, Saudi Arabia

[5] Hitit Univ, Fac Arts & Sci, Dept Phys, Corum, Turkiye

[6] Hitit Univ, Fac Arts & Sci, Dept Chem, Corum, Turkiye

[7] Benemerita Univ Autonoma Puebla, Inst Ciencias, Ctr Quimicadel, 18 sur & Ave San, Claudio 72570, Col San Manuel, Mexico

[8] Benemerita Univ Autonoma Puebla, Fac Ciencias Quim, Ctr Invest, Dept Fisicoquim,Lab QuimicaTeor, Edif FCQ10, 22 Sur & San Claudio,Ciudad Univ, Puebla 72570, Puebla, Mexico

[9] Univ 8 May 1945, Fac Math Informat & Mat Sci, Dept Mat Sci, Lab Computat Chem & Nanostruct, Guelma, Algeria

[10] Univ Monastir, Fac Sci, Quantum & Stat Phys Lab, Monastir 5079, Tunisia

[11] Wuhan Text Univ, Sch Text Sci & Engn, Natl Engn Lab Adv Yarn & Clean Prod, Wuhan 430200, Peoples R China

来源：

MATERIALS CHEMISTRY AND PHYSICS | 2023年 / 309卷

关键词：

DFT-D3; Nanocages-ligands; Adsorptions sites; Charge transfer; IGM-NCI; QTAIM-ELF; DENSITY-FUNCTIONAL THEORY; METAL; PRISTINE; NBO; CLASSIFICATION; NANOPARTICLES; LOCALIZATION; SPECTROSCOPY; (ZNO)(12); ZN12O12;

D O I：

10.1016/j.matchemphys.2023.128364

中图分类号：

T [工业技术];

学科分类号：

08 ;

摘要：

The electron-spin duality and propagation of the active sites of free electrons are of interest for adsorbing the guests and fixing them with strong hydrogen bonds (HB). The coherence of the systems with the guests is one of the main parameters that favor the experimentation of new systems on primary column adsorption phenomena. The stability and the adaptable symmetries in all directions justify the use of a "nanocage" (ZnO) for studying adsorption phenomena. The formation of stable electronic charge transfer paths between sites occupied by very stable atomic orbitals ensures the success of the adsorption of the ligands. Electronic characterization (MES, FMO, DOS, and cationic doping) is used to describe the movement of the intra-Cu-Co/Zn19O20 electrons. The phenomena of charge transfer, stability, types of orbital occupations, adsorption sites, electron migration direction, conductivity, and reactivity of such systems are thoroughly explored. Based on these findings, the efficiency of a Cu-Co/Zn19O20 nanocage to adsorb three different ligands (medical ligands, prostate biomarkers, and antibiotics) is studied. From the reactivity parameter discussions, it is found that the copper or cobalt-doped nanocage-Citric Acid has a strongly electronegative index (4.40 eV and 4.91 eV) and hardness (1.99 eV and 1.82 eV) properties. The Fourier transform infrared analyses and orbital localizations (& alpha; and & beta;) clearly demonstrate that the charge transfer occurs inter-surface, from nanocages to adsorbed ligands. Bader's theory analysis for the adsorption ligands VA (Vinyl Alcohol), CA (Citric Acid), and SMX (Sulfamethoxazole) by the doped copper and cobalt nanocages demonstrates that these systems are much more adequate for adsorbing the ligand antibiotics than the other hosts. The highly adsorbent energy of sulfamethoxazole by Cu-Zn19O20 is equal to-582.86 kJ. mol-1. The IGM-NCI/ELF analyses support these findings, revealing that the Cu/Co-Zn19O20 nanocages adsorb SMX via hydrogen bonding and van der Waals interactions, as they also did in DFT-D3 and FT-IR analyses. LOL analyses support this claim by visualizing single-pair spins in excess surrounding acceptor atoms (O) in the two systems. Molecular dynamics simulations show that SMX is quickly adsorbed by nanocages of Zn19O20 doped with copper (d9) or cobalt (d7).

引用

页数：30