Defect engineering in 1D Ti-W oxide nanotube arrays and their correlated photoelectrochemical performance.

Understanding the nature of interfacial defects of materials is a critical undertaking for the design of high-performance hybrid electrodes for photocatalysis applications. Theoretical and computational endeavors to achieve this have touched boundaries far ahead of their experimental counterparts. However, to achieve any industrial benefit out of such studies, experimental validation needs to be systematically undertaken. In this sense, we present herein experimental insights into the synergistic relationship between the lattice position and oxidation state of tungsten ions inside a TiO2 lattice, and the respective nature of the created defect states. Consequently, a roadmap to tune the defect states in anodically-fabricated, ultrathin-walled W-doped TiO2 nanotubes is proposed. Annealing the nanotubes in different gas streams enabled the engineering of defects in such structures, as confirmed by XRD and XPS measurements. While annealing under hydrogen stream resulted in the formation of abundant Wn+ (n < 6) ions at the interstitial sites of the TiO2 lattice, oxygen- and air-annealing induced W6+ ions at substitutional sites. EIS and Mott-Schottky analyses indicated the formation of deep-natured trap states in the hydrogen-annealed samples, and predominantly shallow donating defect states in the oxygen- and air-annealed samples. Consequently, the photocatalytic performance of the latter was significantly higher than those of the hydrogen-annealed counterparts. Upon increasing the W content, photoelectrochemical performance deteriorated due to the formation of WO3 crystallites that hindered charge transfer through the photoanode, as evident from the structural and chemical characterization. To this end, this study validates the previous theoretical predictions on the detrimental effect of interstitial W ions. In addition, it sheds light on the importance of defect states and their nature for tuning the photoelectrochemical performance of the investigated materials.

Tailoring the reducibility and catalytic activity of CuO nanoparticles for low temperature CO oxidation.

Copper oxide (CuO) nanoparticles have received considerable interest as active and inexpensive catalysts for various gas-solid reactions. The CuO reducibility and surface reactivity are of crucial importance for the high catalytic activity. Herein, we demonstrate that the reducibility and stability of CuO nanoparticles can be controlled and tailored for the high catalytic activity of CO oxidation. The synthesized CuO nanoparticles possessed enhanced reducibility in CO atmosphere at lower reduction temperature of 126 °C compared to 284 °C for that of reference CuO particles. Moreover, the CuO catalysts with tailored reducibility demonstrated a reaction rate of 35 µmol s-1 g-1 and an apparent activation energy of 75 kJ mol-1. Furthermore, the tailored catalysts exhibited excellent long-term stability for CO oxidation for up to 48 h on stream. These readily-reducible CuO nanoparticles could serve as efficient, inexpensive and durable catalysts for CO oxidation at low temperatures.

Rational one-step synthesis of porous PtPdRu nanodendrites for ethanol oxidation reaction with a superior tolerance for CO-poisoning.

Precise fabrication of porous ternary Pt-based nanodendrites is very important for electrochemical energy conversion owing to high surface area and great molecular accessibility of these nanodendrites. Herein, PtPdRu porous nanodendrites (PNDs) were prepared via a facile one-step ultrasonic irradiation approach at room temperature. Intriguingly, the ultrasonic irradiation drove the formation of PtPdRu PNDs with spatially interconnected porous structures, whereas magnetic stirring produced PtPdRu nanoflowers (NFs) with less porosity. The formation mechanism was ascribed to the acoustic cavitation effect and fast-reduction kinetics under sonication. The as-made PtPdRu PNDs displayed a superior catalytic performance towards ethanol oxidation reaction with a high tolerance for CO-poisoning as compared to PtPdRu NFs, PtPd NDs, and commercial Pt/C catalyst.

An efficient eco advanced oxidation process for phenol mineralization using a 2D/3D nanocomposite photocatalyst and visible light irradiations.

Nanocomposites (CNTi) with different mass ratios of carbon nitride (C3N4) and TiO2 nanoparticles were prepared hydrothermally. Different characterization techniques were used including X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), transmission electron spectroscopy (TEM) and Brunauer-Emmett-Teller (BET). UV-Vis DRS demonstrated that the CNTi nanocomposites exhibited absorption in the visible light range. A sun light - simulated photoexcitation source was used to study the kinetics of phenol degradation and its intermediates in presence of the as-prepared nanocomposite photocatalysts. These results were compared with studies when TiO2 nanoparticles were used in the presence and absence of H2O2 and/or O3. The photodegradation of phenol was evaluated spectrophotometrically and using the total organic carbon (TOC) measurements. It was observed that the photocatalytic activity of the CNTi nanocomposites was significantly higher than that of TiO2 nanoparticles. Additionally, spectrophotometry and TOC analyses confirmed that degraded phenol was completely mineralized to CO2 and H2O with the use of CNTi nanocomposites, which was not the case for TiO2 where several intermediates were formed. Furthermore, when H2O2 and O3 were simultaneously present, the 0.1% g-C3N4/TiO2 nanocomposite showed the highest phenol degradation rate and the degradation percentage was greater than 91.4% within 30 min.

Silver Nanoparticles-Decorated Titanium Oxynitride Nanotube Arrays for Enhanced Solar Fuel Generation.

We demonstrate, for the first time, the synthesis of highly ordered titanium oxynitride nanotube arrays sensitized with Ag nanoparticles (Ag/TiON) as an attractive class of materials for visible-light-driven water splitting. The nanostructure topology of TiO2, TiON and Ag/TiON was investigated using FESEM and TEM. The X-ray photoelectron spectroscopy (XPS) and the energy dispersive X-ray spectroscopy (EDS) analyses confirm the formation of the oxynitride structure. Upon their use to split water photoelectrochemically under AM 1.5 G illumination (100 mW/cm2, 0.1 M KOH), the titanium oxynitride nanotube array films showed significant increase in the photocurrent (6 mA/cm2) compared to the TiO2 nanotubes counterpart (0.15 mA/cm2). Moreover, decorating the TiON nanotubes with Ag nanoparticles (13 ± 2 nm in size) resulted in exceptionally high photocurrent reaching 14 mA/cm2 at 1.0 VSCE. This enhancement in the photocurrent is related to the synergistic effects of Ag decoration, nitrogen doping, and the unique structural properties of the fabricated nanotube arrays.

On the nature of defect states in tungstate nanoflake arrays as promising photoanodes in solar fuel cells.

An electrochemical method is presented to study the nature of the defect states in sub-stoichiometric tungsten oxide nanoflake photoanodes used in water splitting. First, stoichiometric/sub-stoichiometric tungstate nanoflake arrays were deliberately developed via annealing under different atmospheres (air, O2, and H2) in different sequences. UV-Vis diffuse reflectance spectra and Tauc analysis indicated the presence of oxygen vacancies, which was also confirmed via XRD and Raman analysis, with samples annealed in an air/O2 sequence resulting in the most stoichiometric monoclinic structures. A defect sensitivity factor was proposed to explain the nature of defects whether they are deep or shallow. Mott-Schottky analysis was used to confirm the expected defect donor densities, as well as to confirm the nature of the developed oxygen vacancy defect states. The tungstate photoanodes were tested in photoelectrochemical water splitting cells and their photoconversion efficiency was demonstrated and discussed in detail.

Dynamic Cross-Linking of Polymeric Binders Based on Host-Guest Interactions for Silicon Anodes in Lithium Ion Batteries.

We report supramolecular cross-linking of polymer binders via dynamic host-guest interactions between hyperbranched ß-cyclodextrin polymer and a dendritic gallic acid cross-linker incorporating six adamantane units for high-capacity silicon anodes. Calorimetric analysis in the solution phase indicates that the given host-guest complexation is a highly spontaneous and enthalpically driven process. These findings are further verified by carrying out gelation experiments in both aqueous and organic media. The dynamic cross-linking process enables intimate silicon-binder interaction, structural stability of electrode film, and controlled electrode-electrolyte interface, yielding enhanced cycling performance. Control experiments using both α, γ-CDp with different cavity sizes and a guest molecule incorporating a single adamantane unit verified that the enhanced cycle life originates from the host-guest interaction between ß-cyclodextrin and adamantane. The impact of the dynamic cross-linking is maximized at an optimal stoichiometry between the two components. Importantly, the present investigation proves that the molecular-level tuning of the host-guest interactions can be translated directly to the cycling performance of silicon anodes.

TiO2 nanotubes with ultrathin walls for enhanced water splitting.

We demonstrate, for the first time, the synthesis of titania nanotubes with ultrathin (3-5 nm) wall thickness. As revealed by the incident photon-to-current collection efficiency (IPCE) and electrochemical impedance spectroscopy measurements, the ultrathin walls, less than the charge carrier diffusion length, were essential to ensure fast and efficient charge carrier collection.

Charge-transfer complexes of 4-methylpiperidine with σ- and π-acceptors.

The solid charge-transfer (CT) molecular complexes formed in the reaction of the electron donor 4-methylpiperidine (4MP) with the σ-electron acceptor iodine and π-acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) have been investigated spectrophotometrically in chloroform at 25 °C. These were characterized through electronic and infrared spectra as well as elemental and thermal analysis. The obtained results showed that the formed solid CT-complexes have the formulas [(4MP) I](+)I(-)3, [(4MP)(DDQ)2] and [(4MP)(TBCHD)] and with TCNQ the adduct [TCMPQDM] is obtained through N-substitution reaction in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements. The formation constant KCT, molar extinction coefficient εCT, free energy change ΔG(0), CT energy ECT and the ionization potential Ip have been calculated for the CT-complexes [(4MP) I](+)I(-)3, [(4MP)(DDQ)2] and [(4MP)(TBCHD)].

Spectrophotometric and thermal studies on the charge--transfer complexes of 4-(aminomethyl) piperidine as donor with σ- and π-electron acceptors.

The spectroscopic characteristics of the solid charge-transfer molecular complexes (CT) formed in the reaction of the electron donor 4-(aminomethyl) piperidine (4AMP) with the σ-acceptor iodine and the π-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) have been studied in chloroform at 25°C. These were investigated through electronic, infrared spectra and thermal analysis as well as elemental analysis. The results show that the formed solid CT-complexes have the formulas [(4AMP)I](+)I3(-), [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)] while in the case of 4AMP-TCNQ reaction, a short-lived CT complex is formed followed by rapid N-substitution by TCNQ forming the final reaction product 7,7,8-tricyano-8-aminomethylpiperidinylquinodimethane [TCAMPQDM] in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements and the thermal analysis confirmed the structure of the obtained compounds. The formation constant kCT, molar extinction coefficient εCT, free energy change ΔG(0) and CT energy ECT have been calculated for the CT-complexes [(4AMP)I](+)I3(-), [(4AMP)(DDQ)2] and [(4AMP)(TBCHD)].

Synthesis, spectroscopic and thermal investigations of solid charge-transfer complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane and the acceptors iodine, TCNE, TCNQ and chloranil.

The solid charge-transfer complexes formed in the reaction of the electron donor 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) with the acceptors iodine, tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) have been isolated. These were characterized through electronic and infrared spectra as well as thermal and elemental analysis. The results show that the formed solid CT-complexes have the formulas [(TMTACN)I]I3, [(TMTACN)(TCNE)5] and [(TMTACN)(TCNQ)3] in full agreement with the known reaction stoichiometries in solution. The chloranil CT-solid complex cannot be isolated in pure form.

Spectroscopic investigation of the charge-transfer interactions between 1,4,7-trimethyl-1,4,7-triazacyclononane and the acceptors iodine, TCNE, TCNQ and chloranil.

The interaction of the interesting polynitrogen cyclic base 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) with the sigma-acceptor iodine and pi-acceptors tetracyanoethylene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and tetrachloro-p-benzoquinone (chloranil) have been studied spectrophotometrically and cyclic voltametrically in chloroform at 20 degrees C. Based on the obtained data, the formed charge-transfer complexes were formulated as [(TMTACN)I](+).I(3)(-), [(TMTACN)(TCNE)(5)], [(TMTACN)(TCNQ)(3)] and [(TMTACN)(chloranil)(3)] where the stoichiometry of the reactions, donor:acceptor molar ratios, were shown to equal 1:2 for iodine complex, 1:3 for chloranil and TCNQ complexes and 1:5 for TCNE complex.

Spectroscopic investigation of the novel charge-transfer complex [(phen)(TCNE)(12)] formed in the reaction of phenacetin with tetracyanoethylene.

The charge-transfer (CT) interaction of the electron donor phenacetin (phen) and the pi-electron acceptor tetracyanoethylene (TCNE) has been studied in CH(2)Cl(2). The results obtained indicate the formation of the novel CT-complex with the general formula [(phen)(TCNE)(12)]. The 1:12 stoichiometry of the reaction was based on photometric titration, elemental analysis, infrared, thermal and cyclic voltametry measurements of the formed CT-complex.