MXene sheets, as new 2D nanomaterials, have been used in many advanced applications due to their superior thin-layered architecture, as well as their capability to be employed as novel nanocontainers for advanced applications. In this research, intercalated Ti 3 C 2 MXene sheets were synthesized through an etching method, and then they were modified with 3aminopropyltriethoxysilane (APTES). Cerium cations (Ce 3+ ) as an eco-friendly corrosion inhibitor were encapsulated within Ti 3 C 2 MXene sheets to fabricate novel self-healing epoxy nanocomposite coatings. The corrosion protection performance (CPP) of Ce 3+ -doped Ti 3 C 2 MXene nanosheets (Ti 3 C 2 MXene-Ce 3+ ) in a 3.5 wt % sodium chloride (NaCl) solution was studied on bare mild steel substrates using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The self-healing CPP of epoxy coatings loaded with 1 wt % undoped and doped Ti 3 C 2 MXene was evaluated using EIS, salt spray, and field emission scanning electron microscopy (FE-SEM) techniques. The introduction of Ti 3 C 2 MXene-Ce 3+ into the corrosive solution and artificially scribed epoxy coating enhanced the total impedance from 717 to 6596 Ω cm 2 and 8876 to 32092 Ω cm 2 , respectively, after 24 h of immersion compared to the control samples.
The polaron introduced by the oxygen vacancy (Vo) dominates many surface adsorption processes and chemical reactions on reduced oxide surfaces. Based on IR spectra and DFT calculations of NO and CO adsorption, we gave two scenarios of polaron-involved molecular adsorption on reduced TiO2(110) surfaces. For NO adsorption, the subsurface polaron electron transfers to a Ti:3d-NO:2p hybrid orbital mainly on NO, leading to the large redshifts of vibration frequencies of NO. For CO adsorption, the polaron only transfers to a Ti:3d state of the surface Ti5c cation underneath CO, and thus only a weak shift of vibration frequency of CO was observed. These scenarios are determined by the energy-level matching between the polaron state and the LUMO of adsorbed molecules, which plays a crucial role in polaron-adsorbate interaction and related catalytic reactions on reduced oxide surfaces.
CO2 adsorption and interaction on rutile TiO2(110) surfaces was studied by UHV-FTIRS combined with theoretical simulations. With increasing CO2 exposure, CO2 adsorbs in succession at the oxygen vacancy (Vo) sites, on the five-coordinated Ti cation (Ti5c) sites and the bridging oxygen (Obr) sites at low temperature. The coupling has occurred between neighboring CO2 adsorbed on Ti5c sites from rather low CO2 coverage (∼0.5 ML), leading the ν3(OCO) asymmetric stretching vibrations to split into two absorption bands in IR spectra. Two kinds of coupled geometries of adjacent CO2 on Ti5c sites are determined by theoretical simulations. For the higher CO2 coverage (∼1.5 ML), the horizontal adsorption configuration along the [11[combining macron]0] azimuth of CO2 adsorbed on Obr sites is identified for the first time using polarization- and azimuth-resolved RAIRS in experiments. The significant deviation of CO2 from the top of Obr sites demonstrates the strong coupling between CO2 adsorbed on Obr and Ti5c sites.
The adsorption and reaction of NO on both the oxidized and reduced single crystal rutile TiO2(110) surfaces were studied in a UHV-FTIRS system at low temperature. The monodentate adsorption configuration of the cis-(NO)2 dimer at bridge oxygen vacancy (Vo) sites was detected for the first time on reduced TiO2(110) surfaces. With the aid of (NO)2 dimer adsorption anisotropy, the bidentate configuration of the cis-(NO)2 dimer on fivefold coordinated Ti5c(4+) cation sites was clearly confirmed. The (NO)2 dimer converts to N2O on Ti5c(4+) cation sites at higher NO dosage on both oxidized and reduced surfaces, rather than at Vo sites. The (NO)2 → N2O conversion is independent of the presence of Vo on TiO2(110) surfaces. To explain the signs of absorption bands of the dimer monodentate configuration, the local optical constant at Vo sites was introduced.
Competitive adsorption of prototype molecules such as (12)CO, (13)CO and CO2 at the two typical fivefold coordinated Ti5c(4+) cation sites of reduced rutile TiO2(110) surfaces was studied in a newly designed UHV-FTIR system. The measured binding energies of (12)CO, (13)CO or CO2 adsorbed at two kinds of Ti5c(4+) sites are different. The molecular occupying probability at these sites depends on the binding energy of the adsorbed molecules; while, the molecular exchanging probability at these sites depends on their binding energy difference due to the presence of competitive adsorption. A simple thermodynamic equilibrium model was proposed to qualitatively interpret the adsorption and competitive adsorption mechanisms. These results will contribute to the elucidation of the (photo)catalytic process on TiO2(110) surfaces.
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