Metal organic framework-assisted copper-modified titania (Cu/TiO2) with abundant exposed active sites and highly accessible pore channels for an enhanced photo-generation of hydrogen.

Metal-doping is a common strategy for establishing active sites on photocatalyst, but appropriately exposing them for maximized atomic utilization remains a great challenge in photocatalytic research. Herein, we propose a metal organic framework (MOF)-assisted approach to synthesis copper-modified titania (Cu-TiO2/Cu) photocatalyst with homogenously distributed and highly accessible active sites in its matrix. Significantly, an MOF precursor, namely NH2-MIL-125, with co-chelation of titania (Ti) and copper (Cu) was subjected to mild calcination, subsequently results in Cu-modified TiO2 with highly accessible channels to its inner surface. These channels provide not only a large reactive surface (>400 m2 g-1); they also enable facile modifying route for the pre-deposited Cu in prior to photoreaction. Specifically, NH3 treatment was applied to partially reduce deposited Cu ions (Cu+ and Cu2+) into Cu nanoparticles, where their interplays realize improved optical properties and charge separation during photoreactions. Furthermore, the NH3-induced Cu nanoparticles could also serve as the adsorptive site for H+, thereby enabling 5629 µmol h-1 g-1 H2 generation over the optimum photocatalyst of Cu20/TiO2/Cu500. Such performance is associated to 35.44 and 1.71-fold improvements compared to pure TiO2 (Cu0/TiO2) and untreated Cu-ion modified TiO2 (Cu20/TiO2), respectively. This work offers a new synthetic strategy for obtaining photocatalyst with evenly distributed and highly accessible active sites, thus improving the commensurability of photocatalytic H2 generation from the industrial perspective.

Nickel-cobalt alloy nanosheet-decorated three-dimensional titanium dioxide nanobelts electrodeposited on titanium meshes for boosting selective nitrate electroreduction to ammonia.

Electrocatalytic nitrate reduction reaction presents a promising avenue for environmentally friendly ammonia (NH3) synthesis and wastewater treatment. An essential aspect to consider is the meticulous design of electrocatalysts. This study explores the utilization of a Ni-Co alloy nanosheet-decorated three-dimensional titanium dioxide (3D-TiO2) nanobelts electrodeposited on titanium meshes (NixCoy@TiO2/TM) for efficient electrocatalytic NH3 production. The optimized Ni1Co3@TiO2/TM electrode achieves a significant NH3 yield of 676.3 ± 27.1 umol h-1 cm-2 with an impressive Faradaic efficiency (FE) of 95.1 % ± 2.1 % in a 0.1 M KOH solution containing 0.1 M NO3- at -0.4 V versus the reversible hydrogen electrode. Additionally, the electrode demonstrates exceptional electrochemical activity for NH3 synthesis in simulated wastewater, delivering an outstanding NH3 yield of 751.6 ± 44.3 umol h-1 cm-2 with a FE of 96.8 % ± 0.4 % at the same potential of -0.4 V. Moreover, the electrode exhibits minimal variation in current density, NH3 yields and FEs throughout the 24-h stability test and the 20-cycle test, demonstrating its excellent stability and durability. This study offers a straightforward electrodeposited approach for the development of 3D-nanostructured alloys as catalysts for NH3 electrosynthesis from nitrates at room temperature.

Efficient solar-driven: Photothermal catalytic reduction of atmospheric CO2 at the gas-solid interface by CuTCPP/MXene/TiO2.

Directly capturing atmospheric CO2 and converting it into valuable fuel through photothermal synergy is an effective way to mitigate the greenhouse effect. This study developed a gas-solid interface photothermal catalytic system for atmospheric CO2 reduction, utilizing the innovative photothermal catalyst (Cu porphyrin) CuTCPP/MXene/TiO2. The catalyst demonstrated a photothermal catalytic performance of 124 µmol·g-1·h-1 for CO and 106 µmol·g-1·h-1 for CH4, significantly outperforming individual components. Density functional theory (DFT) results indicate that the enhanced catalytic performance is attributed to the internal electric field between the components, which significantly enhances carrier utilization. The introduction of CuTCPP reduces free energy of the photothermal catalytic reaction. Additionally, the local surface plasmon resonance (LSPR) effect and high-speed electron transfer properties of MXene further boost the catalytic reaction rate. This well-designed catalyst and catalytic system offer a simple method for capturing atmospheric CO2 and converting it in-situ through photothermal catalysis.

The photocatalytic wastewater hydrogen production process with superior performance to the overall water splitting.

The utilization of a cost-free sacrificial agent is a novel approach to significantly enhance the efficiency of photocatalytic hydrogen (H2) production by water splitting. Wastewater contains various organic pollutants, which have the potential to be used as hole sacrificial agents to promote H2 production. Our studies on different pollutants reveals that not all pollutants can effectively promote H2 production. However, when using the same pollutants, not all photocatalysts achieved a higher H2 evolution rate than pure water. Only when the primary oxidizing active species of the photocatalyst are •OH radicals, which are generated by photogenerated holes, and when the pollutants are easily attacked and degraded by •OH radicals, can the production of H2 be effectively promoted. It is noteworthy that the porous brookite TiO2 photocatalyst exhibits a significantly higher H2 evolution rate in Reactive Red X-3B and Congo Red, reaching as high as 26.46 mmol⋅g-1⋅h-1 and 32.85 mmol⋅g-1 ⋅h-1, respectively, which is 2-3 times greater than that observed in pure water and is 10 times greater than most reported studies. The great significance of this work lies in the potential for efficient H2 production through the utilization of wastewater.

Ce-doped TiO2 supported RuO2 as efficient catalysts for the oxidation of HCl to Cl2.

Reducing the cost of RuO2/TiO2 catalysts is still one of the urgent challenges in catalytic HCl oxidation. In the present work, a Ce-doped TiO2 supported RuO2 catalyst with a low Ru loading was developed, showing a high activity in the catalytic oxidation of HCl to Cl2. The results on some extensive characterizations of both Ce-doped TiO2 carriers and their supported RuO2 catalysts show that the doping of Ce into TiO2 can effectively change the lattice parameters of TiO2 to improve the dispersion of the active RuO2 species on the carrier, which facilitates the production of surface Ru species to expose more active sites for boosting the catalytic performance even under some harsh reaction conditions. This work provides some scientific basis and technical support for chlorine recycling.

Cu/TiO2 adsorbents modified by air plasma for adsorption-oxidation of H2S.

In this study, non-thermal plasma (NTP) was employed to modify the Cu/TiO2 adsorbent to efficiently purify H2S in low-temperature and micro-oxygen environments. The effects of Cu loading amounts and atmospheres of NTP treatment on the adsorption-oxidation performance of the adsorbents were investigated. The NTP modification successfully boosted the H2S removal capacity to varying degrees, and the optimized adsorbent treated by air plasma (Cu/TiO2-Air) attained the best H2S breakthrough capacity of 113.29 mg H2S/gadsorbent, which was almost 5 times higher than that of the adsorbent without NTP modification. Further studies demonstrated that the superior performance of Cu/TiO2-Air was attributed to increased mesoporous volume, more exposure of active sites (CuO) and functional groups (amino groups and hydroxyl groups), enhanced Ti-O-Cu interaction, and the favorable ratio of active oxygen species. Additionally, the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results indicated the main reason for the deactivation was the consumption of the active components (CuO) and the agglomeration of reaction products (CuS and SO42-) occupying the active sites on the surface and the inner pores of the adsorbents.

Effects of surface fluoride modification on TiO2 for the photocatalytic oxidation of toluene.

In the present study, we investigated the influence of surface fluorine (F) on TiO2 for the photocatalytic oxidation (PCO) of toluene. TiO2 modified with different F content was prepared and tested. It was found that with the increasing of F content, the toluene conversion rate first increased and then decreased. However, CO2 mineralization efficiency showed the opposite trend. Based on the characterizations, we revealed that F substitutes the surface hydroxyl of TiO2 to form the structure of Ti-F. The presence of the appropriate amount of surface Ti-F on TiO2 greatly enhanced the separation of photogenerated carriers, which facilitated the generation of ·OH and promoted the activity for the PCO of toluene. It was further revealed that the increase of only ·OH promoted the conversion of toluene to ring-containing intermediates, causing the accumulation of intermediates and then conversely inhibited the ·OH generation, which led to the decrease of the CO2 mineralization efficiency. The above results could provide guidance for the rational design of photocatalysts for toluene oxidation.

Singlet Oxygen Photocatalytic Generation by Silanized TiO2 Nanoparticles.

A commercial TiO2 sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by FTIR and solid-state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N2 physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV-vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti3+ defects localized in the sub-surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O2 is efficiently inhibited even under UV irradiation. However, the amount of Ti3+ centers appears to be correlated with the singlet oxygen (1O2) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by 1O2, occurred with higher selectivity when TiO2 was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample 1O2 may be generated through Förster-type energy transfer from excited sub-surface Ti3+ centers.

Surface coating engineering of titanate anodes based on tannic acid-formaldehyde polymer chelating bismuth ions for advanced sodium-ion capacitors.

As a battery-type anode material for sodium ion capacitors (SICs), titanate (H2Ti2O5·H2O, HTO) exhibits good rate capability due to its layered structure, easy to insert Na+ ions and low potential during sodium-ion storage. However, the structure is unstable due to the lattice distortion resulting from the irreversible embedment of Na+ in the process of sodium storage. So there is a significant mismatch between the dynamic reaction of the HTO anode and the capacitive cathode. Surface coating engineering is a useful strategy for stabilizing the HTO structure, which is critical for improving the kinetic response. In this work, a surface coating technique is designed to enhance the surface of HTO nanoarrays on titanium foil by using the oligomers of tannic acid formaldehyde polymer (TAF) chelated Bi3+ ions (Bi-TAF). As a binder-free anode, HTO coated with Bi-TAF (HTO@Bi-TAF) exhibits more excellent capacity (335.2 mA h g-1, 0.1 A g-1), rate capability (212.3 mA h g-1, 2.0 A g-1), and cycle stability (97 % capacity maintenance following 2000 cycles at 1.0 A g-1) than HTO and HTO coated with TAF (HTO@TAF). At the sweep rate of 1.0 mV s-1, the kinetic investigation reveals that the capacitance contribution of HTO@Bi-TAF is 86 %. The SICs exhibit a significant energy/power density (89.4 Wh kg-1/250 W kg-1). This work shows that the Bi-TAF polymer coating has a dual effect of rate capability improvement and structural protection on the prepared HTO. This results in a reasonable and effective surface coating strategy that provides outstanding rate capability and extended cycle performance of titanium-based anode materials for SICs.

Artificial synapses based on HfOx/TiOy memristor devices for neuromorphic applications.

As a result of enormous progress in nanoscale electronics, interest in Artificial Intelligence (AI) supported systems has also increased greatly. These systems are typically designed to process computationally intensive data. Parallel processing neural network architectures are particularly noteworthy for their ability to process dense data at high speeds, making them suitable candidates for AI algorithms. Due to their ability to combine processing and memory functions in a single device, memristors offer a significant advantage over other electronic platforms in terms of area scaling efficiency and energy savings. In this study, single-layer and bilayer metal-oxide HfOx and TiOy memristor devices inspired by biological synapses were fabricated by pulsed laser and magnetron sputtering deposition techniques in high vacuum with different oxide thicknesses. The structural and electrical properties of the fabricated devices were analysed using X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), and standard two-probe electrical characterization measurements. The stoichiometry and degree of oxidation of the elements in the oxide material for each thin film were determined. Moreover, the switching characteristics of the metal oxide upper layer in bilayer devices indicated its potential as a selective layer for synapse. The devices successfully maintained the previous conductivity values, and the conductivity increased after each pulse and reached its maximum value. Furthermore, the study successfully observed synaptic behaviours with long-term potentiation (LTP), long-time depression (LTD), paired-pulse facilitation (PPF), and spike-timing-dependent plasticity (STDP), showcasing potential of the devices for neuromorphic computing applications.

Regulation of the Buried Interface to Achieve Efficient HTL-Free All-Inorganic CsPbI2Br-Based Perovskite Solar Cells.

The large voltage loss (Vloss) mainly stems from the mismatch between the perovskite film and electron transport layer in CsPbI2Br-based all-inorganic perovskite solar cells (I-PSCs), which restricts the power conversion efficiency (PCE) of devices. To address this issue, potassium benzoate (BAP) is first introduced as a bifunctional passivation material to regulate the TiO2/CsPbI2Br interface, reduce the Vloss, and improve the photovoltaic performance of CsPbI2Br-based I-PSCs. Eventually, the champion PCE of CsPbI2Br-based I-PSCs without a hole transport layer modified by BAP (Target-PSCs) improves to 14.90% from the 12.14% of reference PSCs. The open-circuit voltage (Voc) increases to 1.27 V from the initial 1.14 V after BAP modification. A series of characterizations show that BAP modification can not only optimize the energy level alignment of I-PSCs but also passivize the surface defects caused by uncoordinated Cs+/Pb2+. Moreover, the Target-PSCs without encapsulation demonstrate better thermal stability, which can maintain 107.6% of the original PCE after annealing at 160 °C for 140 min in humid air. While the reference PSCs only maintain 76.5% of their initial PCE after annealing at the same process. This work provides a simple strategy to modify the buried interface and improve the performance of CsPbI2Br-based I-PSCs.

Improved surface acidity of CeO2/TiO2 catalyst by Cu doping to enhance the SCR catalytic activity.

The catalyst is based on CeO2 cannot be widely used in SCR reaction because of its poor NH3 adsorption performance. In this study, Cu-doped CeTi catalyst was designed. The results show that the CeTiCu0.3 has a wide active temperature window of 200-450 °C in NH3-SCR reaction, and NO conversion is > 80%. This is mainly due to the fact that Cu doping provides more acidic sites on the surface of CeTi catalyst, especially the increase of Lewis acid sites is more obvious. NH3-TPD showed that CeTiCu0.3 had a large NH3 adsorption capacity and was mainly adsorbed at Lewis acid sites. In situ DRIFTs results show that NH3 first adsorbs on the Lewis acid site of catalyst in coordination state and reacts with gaseous NOx, while NOx adsorbed on catalyst surface has low reactivity. Therefore, the CeTiCu0.3 catalyst is mainly controlled by the Eley-Rideal mechanism. More Lewis acid sites, and abunda nt Cu2+/Cu+ and Ce4+/Ce3+ formed Cu2+, Ce3+ and surface reactive oxygen species are the main reasons for the excellent catalytic performance of CeTiCu.

Ru Nanoparticles Encapsulated by Defective TiO2 Boost the Hydrogen Oxidation/ Evolution Reaction.

The development of efficient and durable electrocatalysts for the alkaline hydrogen oxidation/evolution reaction is crucial for anion exchange membrane fuel cells/water electrolyzers. However, designing such electrocatalysts poses a challenge due to the need for optimizing various adsorbates. Herein, highly dispersed Ru nanoparticles catalysts is reported encapsulated and supported by defective anatase phase of titanium dioxide (named as Ru NPs/def-TiO2(A)) for boosting hydrogen-cycle electrocatalysis with robust anti-CO-poisoning in alkaline conditions. The Ru NPs/def-TiO2(A) achieves a high-quality activity of 7.65 A mgRu -1, which is 23.2 and 9.5-fold higher than commercial Ru/C and Pt/C in alkaline HOR. Moreover, this catalyst exhibits an outstanding overpotential of 21 mV at 10 mA cm-2 in alkaline HER. Hydrogen underpotential deposition (Hupd) and CO stripping experiments demonstrate that Ru NPs/def-TiO2(A) has the optimized H*, OH*, and CO* adsorption strength, enabling the Ru NPs/def-TiO2(A) catalyst to display excellent and robust HOR/HER performance under alkaline conditions. Using density functional theory calculations, the enhanced HOR performance mechanism for the Ru NPs/def-TiO2(A) catalyst originates from the TiO2 step face in contact with the Ru nanoparticles, indicating that the kinetics of water formation are considerably more favorable at the Ru NPs/def-TiO2(A) interface.

Breaking the Lithiation Barrier via Tailored-Design Facile Kinetic Pathways in TiO2(B) Realizing 50C Ultrafast Charging.

As a promising anode material for fast charging lithium-ion batteries, bronze-phase titanium dioxide (TiO2(B)) still faces the challenge of sluggish Li+ diffusion kinetics in the solid phase during lithiation/delithiation processes. Herein, a facile synthetic strategy has been proposed to optimize the microstructure of TiO2(B), which enables facilitated lithiation and therefore significantly improved rate performance. The rice-granular nanoparticles with precisely controlled aspect ratios (AR) can be obtained via manipulating the ligand concentrations that affect nucleation and oriented attachment processes, as well as adjusting the calcination temperatures to control the Oswald ripening process. As a result, the smaller ab plane in rice-granular TiO2(B) enhances Li+ diffusion efficiency on C' site and inhibits the inhomogeneity of Li+ between inter and inside particles. Benefiting from breaking the Li+ diffusion kinetics, the rice-granular TiO2(B) maintains a high specific capacity of 159.5 mAh g-1 at 50C, with an excellent capacity retention ratio of 93.67% after 5000 cycles at 10C. This work provides an efficient and simple strategy to minimize the challenging lithiation paths in TiO2(B) anode, and offers new opportunities for high rate battery design.

Enhanced virucidal activity of facet-engineered Cu-doped TiO2 nanorods under visible light illumination.

Crystal facet engineering has emerged as a promising approach to enhance photocatalytic activity of semiconductors by preferentially accumulating charge carriers (electrons and holes) on specific facets. This facilitates efficient electron and hole transfer across the semiconductor/cocatalyst interface, enabling their transport to the cocatalyst surface for redox reactions. In this study, three Cu-doped TiO2 nanorods with small, medium, and large ratios of reductive {110} to oxidative {111} facets were synthesized (namely Cu-TiO2-SR, Cu-TiO2-MR, and Cu-TiO2-LR, respectively). These materials were comparatively evaluated for the inactivation of phiX174 bacteriophage under visible light illumination. Notably, Cu-TiO2-LR demonstrated an outstanding inactivation rate of phiX174 (0.42 log inactivation/min), approximately 11.8 times higher than that of Cu-TiO2-SR. Photo- and electrochemical analyses revealed that Cu-TiO2-LR exhibited superior electron/hole separation efficiency, leading to enhanced Cu redox reactions. Various experiments, encompassing viral inactivation tests with different additives, protein oxidation assays, and DNA damage assessments, indicated that Cu(III) is the major virucidal species responsible for the phiX174 inactivation by illuminated Cu-TiO2-LR. Under visible light illumination, Cu-TiO2-LR also showed excellent reusability and minimal activity loss in the presence of humic acid and inorganic anions, as well as general microbicidal effects on other viral and bacterial species.

Mechanisms of enhanced performance in Zr4+/Ta5+ codoped rutile-TiO2 ceramics via broadband dielectric spectroscopy.

Aliovalent dopant codoped rutile-TiO2 materials have garnered attention due to their excellent performance properties, characterized by low loss tangent (tanδ), high dielectric permittivity (ε'), and stable ε' over a broad temperature range. This performance is primarily due to the electron-pinned defect-dipoles (EPDDs) of the complex defects [Formula: see text]Ti3+-[Formula: see text]Ti3+BTi. Notably, the excellent dielectric properties in ZrxTa2.5%Ti0.975-xO2 (Zr-TTO) ceramics can be achieved using the traditional mixed oxide method without the EPDDs, due to the absence of A3+ (acceptor doping ions). Instead, the existence of localized free electrons and oxygen vacancies ([Formula: see text]) in Zr-TTO structures, due to doping ions and the sintering process, was confirmed by X-ray photoelectron and Raman spectroscopies. These ceramics exhibited ε'~ 2 × 104 and tanδ < 0.03 at 1 kHz and 25 °C in the 2.5-10%Zr-TTO samples. Moreover, all ceramics demonstrated a maximum ε' change (∆ε') of less than ±15% over the temperature range suitable for X7R and X8R type ceramic capacitors. Significantly, the change in ε' related to relative humility was calculated to be less than ±0.5% over the range of 50-95% RH, indicating the environmental stability of the dielectric properties, which is essential for capacitor applications. Investigations suggested that at least four mechanisms contributed to this system: the intrinsic effect of ionic polarization, Ti4+ · e- -[Formula: see text]- Ti4+ · e- and Ti4+ · e- - [Formula: see text] defects, interfacial polarization at insulating grain boundaries, and non-Ohmic contact between the surface sample and the metal electrode.

Green ternary composite of graphitic carbon nitride/TiO2/ polyorthoanisidine for the enhanced photocatalytic treatment of Direct Red 28 for industrial water treatment solutions.

Industrial dye effluent causes significant risks to the environment. The present study was focused on photocatalytic degradation of the dye Direct Red 28 using a ternary composite of graphitic carbon nitride, TiO2, and polyorthoanisidine (g-C3N4/TiO2/POA), prepared by in-situ oxidative polymerization o-anisidine. The synthesized composite g-C3N4/TiO2/POA properties were characterized using different analytical techniques. X-ray diffraction (XRD) results revealed the prominent pattern of TiO2 and g-C3N4 in the composite peak at 2θ° while Fourier transform infrared (FTIR) results provided the confirmation peaks for g-C3N4/TiO2/POA and POA at 1,110 cm-1 and 1,084 cm-1 for C-O-C ether. Scanning electron microscopy (SEM) demonstrated an increase in the average size of the composite up to 428 nm. The energy-dispersive X-ray spectroscopy (EDX) spectrum provided the weight percentages of the C, O, and Ti in the composite were 8.5%, 45.69%, and 45.81%, respectively. The photocatalytic degradation of Direct Red 28 dye under UV irradiation using a composite showed that 86% Direct Red 28 dye was degraded by a 30 mg/L dose of g-C3N4/TiO2/POA in 240 min at pH 2. After four consecutive cycles, the utilized composite showed 79% degradation of Direct Red 28, demonstrating the stability and effectiveness of the g-C3N4/TiO2/POA photocatalyst. The high reusability and efficiency of the g-C3N4/TiO2/POA composite are due to increased light absorption range and reduced e-/h+ recombination rate in the presence of g-C3N4 and POA.

Characterization of exopolysaccharide / starch composite film incorporated with TiO2 nanoparticles and its application in chilled meat preservation.

Multifunctional food packaging composite films were prepared using Pediococcus acidilactici J1 exopolysaccharide (EPS), potato starch (PS) and TiO2 nanoparticles by casting method. The microstructure, physicochemical properties and antibacterial activity of EPS/PS composite films with different weight ratio of TiO2 nanoparticles were characterized. Transmission electron microscope (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) revealed the uniform distribution of TiO2 nanoparticles in the EPS/PS matrix. Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) results indicated that the interaction between polymers and nanoparticles through non-covalent bonds. When TiO2 nanoparticles were added at 1 % (wt), the composite film had higher barrier properties against water vapor and UV-vis light, and better mechanical properties then EPS/PS film. Notably, EPS/PS/1%TiO2 composite film exhibited good antioxidant and antibacterial activity against Escherichia coli and Staphylococcus aureus. Through the analysis of the quality indexes and microbial community structure during the storage of chilled meat, the composite film slowed the oxidation rate of chilled meat and inhibited the growth of dominant spoilage bacteria, effectively extending its shelf life. All results suggested that EPS/PS/1%TiO2 composite film could serve as an effective packaging material for chilled meat, providing a novel approach to solve its limited shelf-life problem.

In Situ Driven Formation of Anatase/Brookite/Rutile Heterojunction N/TiO2 Nanocrystals as Sustainable Visible-Light Catalysts.

Visible-light active anatase/brookite/rutile (A/B/R) ternary N-doped titania (N/TiO2) crystals are successfully prepared by a facile sol-gel method using titanium butoxide and benign N-dopant source, guanidinium chloride. Systematically varying the aging time (1, 4, 8, and 12 d), its influence on physicochemical properties of as-obtained spherical heterojunction nanomaterials is studied. Detailed characterizations confirm that a substantial amount of anatase (88% to 50%) is transformed to rutile (2% to 38%) via intermediate brookite phase (9% to 25%) as the function of aging time; not only the A/B/R phase content of the samples is tuned by sol-gel aging time of the precursors solution but also their optical-response and methylene blue photocatalytic properties are profoundly dictated. Notably under visible-light irradiation, the photostable rutile rich mesoporous A/B/R triphasic N/TiO2 (50% A, 12% B, 38% R) aged for 12 d demonstrates higher degradation activity (97%) with a faster degradation rate (0.033 min-1) than both lesser aged N/TiO2 and undoped titania. This enhancement is attributed to the synergistic effect of interstitial-N-doping and optimal A/B/R interfacial charge transfer that leads to higher light absorption, lower bandgap energy and well-separated charge carriers. The current work provides a new perspective for designing highly active visible-light heterostructure nanomaterials with controllable phase composition.

Shell-by-Shell functionalized nanoparticles as radiosensitizers and radioprotectors in radiation therapy of cancer cells and tumor spheroids.

Shell-by-Shell (SbS)-functionalized NPs can be tailor-made by combining a metal oxide NP core of choice with any desired phosphonic acids and amphiphiles as 1st or 2nd ligand shell building blocks. The complementary composition of such highly hierarchical structures makes them interesting candidates for various biomedical applications, as certain active ingredients can be incorporated into the structure. Here, we used TiO2 and CoFe2O4 NPs as drug delivery tools and coated them with a hexadecylphosphonic acid and with hexadecyl ammonium phenolates (caffeate, p-coumarate, ferulate), that possess anticancer as well as antioxidant properties. These architectures were then incubated in 2D and 3D cell cultures of non-tumorigenic and tumorigenic breast cells and irradiated to study their anticancer effect. It was found that both, the functionalized TiO2 and CoFe2O4 NPs acted as strong protective agents in non-tumorigenic spheroids. In contrast, the functionalized CoFe2O4 NPs induce a higher damage in irradiated tumor spheroids compared to the functionalized TiO2 NPs. CoFe3O4 NPs act additionally as radiosensitizing agents to the tumor spheroids. The radio-enhancement of the CoFe2O4 NPs is due to the generation of highly toxic hydroxyl radicals during X-ray irradiation. The irradiation exposed the CoFe2O4 surface, releasing the anticancer drugs into the cytoplasm and making the surface Co2+ ions accessible. These surface ions catalyze the Fenton reaction. This combination of radiosensitizer and anticancer drug delivery proved to be a very effective nanotherapeutic in 2D and 3D cell cultures of breast cancer cells.