A deficiency in the photoelectrical dynamics at the interface due to the surface traps of the TiO2 electron transport layer (ETL) has been the critical factor for the inferiority of the power conversion efficiency (PCE) in the perovskite solar cells. Despite its excellent energy level alignment with most perovskite materials, its large density of surface defect as a result of sub lattice vacancies has been the critical hurdle for an efficient photovoltaic process in the device. Here, we report that atoms thick 2D TiS2 layer grown on the surface of a (001) faceted and single-crystalline TiO2 nanograss (NG) ETL have effectively passivated the defects, boosting the charge extractability, carrier mobility, external quantum efficiency, and the device stability. These properties allow the perovskite solar cells (PSCs) to produce a PCE as high as 18.73% with short-circuit current density (Jsc), open-circuit voltage (Voc), and fill-factor (FF) values as high as 22.04 mA/cm2, 1.13 V, and 0.752, respectively, a 3.3% improvement from the pristine TiO2-NG-based PSCs. The present approach should find an extensive application for controlling the photoelectrical dynamic deficiency in perovskite solar cells.
Nickel (Ni) catalysts supported on mesoporous graphitic carbon nitride (mpg-C3N4) were synthesized through simple impregnation method with air and nitrogen calcination atmosphere for CO methanation. The effects of pretreatment gas on catalyst structure, surface characteristics, and Ni species reducibility were investigated. Under air-calcination condition, the increase in specific surface area of the catalyst can be ascribed to the creation of mesopores and exfoliation of bulk mpg-C3N4 to form thin sheets. However, excessive Ni content on the catalyst accelerated the decomposition of the mpg-C3N4 support during calcination. The catalysts calcined in nitrogen showed lower surface area and fewer number of pores compared to air-treatment. The Ni/mpg-C3N4 catalyst calcined in air with Ni loading 10% exhibited enhanced medium-temperature activity for CO methanation with 79.7% CO conversion and 73.9% CH4 selectivity. This finding can be explained by the formation of mpg-C3N4 thin sheets, which increased the number of catalyst active sites. The CO methanation performance of Ni/mpg-C3N4 catalysts calcined in air was superior to those calcined in nitrogen. Interestingly, CO2 formed by water-gas shift reaction at 320 °C also contributed to the overall methane formation through CO2 methanation. Therefore, mpg-C3N4 thin sheets can be an interesting support for nickel catalyst for CO x methanation.
Although solid-state Li-metal batteries (LMBs) featuring polymer-based solid electrolytes might one day replace conventional Li-ion batteries, the poor Li-ion conductivity of solid polymer electrolytes at low temperatures has hindered their practical applications. Herein, we describe the first example of using a co-precipitation method in a Taylor flow reactor to produce the metal hydroxides of both the Ga/F dual-doped Li7La3Zr2O12 (Ga/F-LLZO) ceramic electrolyte precursors and the Li2MoO4-modified Ni0.8Co0.1Mn0.1O2 (LMO@T-LNCM 811) cathode materials for LMBs. The Li/Nafion (LiNf)-coated Ga/F-LLZO (LiNf@Ga/F-LLZO) ceramic filler was finely dispersed in the poly(vinylidene fluoride)/polyacrylonitrile/lithium bis(trifluoromethanesulfonimide)/succinonitrile matrix to give a trilayer composite polymer electrolyte (denoted "Tri-CPE") through a simple solution-casting. The bulk ionic conductivity of the Tri-CPE at room temperature was approximately 4.50 × 10-4 S cm-1 and exhibited a high Li+ ion transference number (0.84). It also exhibits a broader electrochemical window of 1-5.04 V versus Li/Li+. A full cell based on a CR2032 coin cell containing the LMO@T-LNCM811-based composite cathode, when cycled under 1 C/1 C at room temperature for 300 cycles, achieved an average Columbic efficiency of 99.4% and a capacity retention of 89.8%. This novel fabrication strategy for Tri-CPE structures has potential applications in the preparation of highly safe high-voltage cathodes for solid-state LMBs.
Morphological surface modifications have been reported to enhance the performance of biomedical implants. However, current methods of introducing graded porosity involves postprocessing techniques that lead to formation of microcracks, delamination, loss of fatigue strength, and, overall, poor mechanical properties. To address these issues, we developed a microwave sintering procedure whereby pure titanium powder can be readily densified into implants with graded porosity in a single step. Using this approach, surface topography of implants can be closely controlled to have a distinctive combination of surface area, pore size, and surface roughness. In this study, the effect of various surface topographies on in vitro response of neonatal rat calvarial osteoblast in terms of attachment and proliferation is studied. Certain graded surfaces nearly double the chance of cell viability in early stages (∼one month) and are therefore expected to improve the rate of healing. On the other hand, while the osteoblast morphology significantly differs in each sample at different periods, there is no straightforward correlation between early proliferation and quantitative surface parameters such as average roughness or surface area. This indicates that the nature of cell-surface interactions likely depends on other factors, including spatial parameters.
Effective heat dissipation and real-time temperature monitoring are crucial for ensuring the long-term stable operation of modern, high-performance electronic products. This study proposes a silicon rubber polydimethylsiloxane (PDMS)-based nanocomposite with a rapid thermal response and high thermal conductivity. This nanocomposite enables both rapid heat dissipation and real-time temperature monitoring for high-performance electronic products. The reported material primarily consists of a thermally conductive layer (Al2O3/PDMS composites) and a reversible thermochromic layer (organic thermochromic material, graphene oxide, and PDMS nanocoating; OTM-GO/PDMS). The thermal conductivity of OTM-GO/Al2O3/PDMS nanocomposites reached 4.14 W m-1 K-1, reflecting an increase of 2200% relative to that of pure PDMS. When the operating temperature reached 35, 45, and 65 °C, the surface of OTM-GO/Al2O3/PDMS nanocomposites turned green, yellow, and red, respectively, and the thermal response time was only 30 s. The OTM-GO/Al2O3/PDMS nanocomposites also exhibited outstanding repeatability and maintained excellent color stability over 20 repeated applications.
Broadening light absorption and improving charge carrier separation are very critical to boost the water splitting efficiency in photoelectrochemical (PEC) systems. We herein reported a heterostructured photoanode consisting of BiVO4 and eco-friendly, near-infrared (NIR) CuInSeS@ZnS core-shell quantum dots (QDs) for PEC water oxidation. The decoration of core-shell QDs concurrently extends the absorption range of BiVO4 from the ultraviolet-visible to NIR region and promotes the effective separation and transfer of photo-excited electrons and holes. Without any sacrificial agents and co-catalysts, the as-fabricated NIR core-shell QDs/BiVO4 heterostructured photoanodes exhibit an approximately fourfold higher photocurrent density than that of the bare BiVO4, up to 3.17 mA cm-2 at 1.23 V versus the reversible hydrogen electrode. It is revealed that both a suitable band alignment and an intimate interfacial junction between QDs and BiVO4 are the main factors that result in enhanced charge separation and transfer efficiencies. We also highlight that the NIR CISeS QDs passivated with a ZnS shell can suppress the non-radiative recombination and enhance the stability of the QD photoanodes for optimized PEC performance. This work provides a facile and effective approach to boost the water oxidation efficiency of semiconductor photoanodes via utilizing NIR core-shell QDs as a light sensitizer and charge carrier separator.
In this study, the spontaneous microstructure tuning of TiO2 was observed by aging the ethanol/water TiO2 paste for up to 20 days at ambient conditions. A dynamic light scattering study reveals that it formed the outstanding reproducible TiO2 microstructure with a ∼200 nm average particle size and stabilizes in 6 to 20 days under an ambient atmosphere. Interestingly, the as-deposited day 15 sample spontaneously changed its crystallinity upon keeping the paste at ambient conditions; meanwhile the day 0 sample showed an amorphous structure. A dense, uniform, and stable TiO2 electrode was cast on a fluorine doped-tin oxide substrate using the electrospray technique. We exploit the spontaneous evolution of the TiO2 nanopowder to revisit the fabrication procedure of the TiO2 photoelectrode for dye-sensitized solar cells (DSSCs). The controlled microstructure TiO2 film was used in DSSCs, which, to the best of our knowledge, achieved the highest power conversion efficiency of 9.65% using N719 dye in sensitizing the TiO2 photoanode.
Magnetite nanoparticles were successfully synthesized and effectively employed as heterogeneous catalyst for hydrogenation of ketone moiety to alcohol moiety by NaBH4 under the microwave radiation process. The improvement was achieved in percent recovery of isopropyl alcohol by varying and optimizing reaction time, power of microwave radiations and amount of catalyst. The catalytic study revealed that acetone would be converted into isopropyl alcohol (IPA) with 99.5% yield in short period of reaction time, using 10 μg of magnetite NPs (Fe3O4). It was observed that the catalytic hydrogenation reaction, followed second-order of reaction and the Langmuir-Hinshelwood kinetic mechanism, which elucidated that both reactants get adsorb onto the surface of silica coated magnetite nanocatalyst to react. Consequently, the rate-determining step was the surface reaction of acetone and sodium borohydride. The current study revealed an environment friendly conversion of acetone to IPA on the basis of its fast, efficient, and highly economical method of utilization of microwave irradiation process and easy catalyst recovery.
Chitosan-based hemostats are promising candidates for immediate hemorrhage control. However, they have some disadvantages and require further improvement to achieve the desired hemostatic efficiency. Here, a series of 1% Ga2O3-containing mesoporous bioactive glass-chitosan composite scaffolds (Ga-MBG/CHT) were constructed by the lyophilization process and the effect of various concentrations of Ga-MBG (10, 30, and 50 wt %) on the hemostatic function of the CHT scaffold was assessed as compared to that of Celox Rapid gauze (CXR), a current commercially available chitosan-coated hemostatic gauze. The prepared scaffolds exhibited >79% porosity and showed increased water uptake compared to that in CXR. The results of coagulation studies showed that pure CHT and composite scaffolds exhibited increased hemostatic performance with respect to CXR. Furthermore, the composite scaffold with the highest Ga-MBG content (50 wt %) had increased capability to enhancing thrombus generation, blood clotting, and platelet adhesion and aggregation than that of the scaffold made of pure CHT. The antibacterial efficacy and biocompatibility of the prepared scaffolds were also assessed by a time-killing assay and an Alamar Blue assay, respectively. Our results show that the antibacterial effect of 50% Ga-MBG/CHT was more pronounced than that of CHT and CXR. The cell viability results also demonstrated that Ga-MBG/CHT composite scaffolds had good biocompatibility, which facilitates the spreading and proliferation of human dermal fibroblast cells even with 50 wt % Ga-MBG loading. These results suggest that Ga-MBG/CHT scaffolds could be a promising hemostatic candidate for improving hemostasis in critical situations.
Transition metal chalcogenides (TMCs) have gained worldwide interest owing to their outstanding renewable energy conversion capability. However, the poor mechanical flexibility of most existing TMCs limits their practical commercial applications. Herein, triggered by the recent and imperative synthesis of highly ductile α-Ag2S, an effective approach based on evolutionary algorithm and ab initio total-energy calculations for determining stable, ductile phases of bulk and two-dimensional Ag x Se1-x and Ag x Te1-x compounds was implemented. The calculations correctly reproduced the global minimum bulk stoichiometric P212121-Ag8Se4 and P21/c-Ag8Te4 structures. Recently reported metastable AgTe3 was also revealed but it lacks dynamical stability. Further single-layered screening unveiled two new monolayer P4/nmm-Ag4Se2 and C2-Ag8Te4 phases. Orthorhombic Ag8Se4 crystalline has a narrow, direct band gap of 0.26 eV that increases to 2.68 eV when transforms to tetragonal Ag4Se2 monolayer. Interestingly, metallic P21/c-Ag8Te4 changes to semiconductor when thinned down to monolayer, exhibiting a band gap of 1.60 eV. Present findings confirm their strong stability from mechanical and thermodynamic aspects, with reasonable Vickers hardness, bone-like Young's modulus (E) and high machinability observed in bulk phases. Detailed analysis of the dielectric functions ε(ω), absorption coefficient α(ω), power conversion efficiency (PCE) and refractive index n(ω) of monolayers are reported for the first time. Fine theoretical PCE (SLME method ∼11-28%), relatively high n(0) (1.59-1.93), and sizable α(ω) (104-105 cm-1) that spans the infrared to visible regions indicate their prospects in optoelectronics and photoluminescence applications. Effective strategies to improve the temperature dependent power factor (PF) and figure of merit (ZT) are illustrated, including optimizing the carrier concentration. With decreasing thickness, ZT of p-doped Ag-Se was found to rise from approximately 0.15-0.90 at 300 K, leading to a record high theoretical conversion efficiency of ∼12.0%. The results presented foreshadow their potential application in a hybrid device that combines the photovoltaic and thermoelectric technologies.
To overcome the critical limitations of liquid-electrolyte-based dye-sensitized solar cells, quasi-solid-state electrolytes have been explored as a means of addressing long-term device stability, albeit with comparatively low ionic conductivities and device performances. Although metal oxide additives have been shown to augment ionic conductivity, their propensity to aggregate into large crystalline particles upon high-heat annealing hinders their full potential in quasi-solid-state electrolytes. In this work, sonochemical processing has been successfully applied to generate fine Co3O4 nanoparticles that are highly dispersible in a PAN:P(VP-co-VAc) polymer-blended gel electrolyte, even after calcination. An optimized nanocomposite gel polymer electrolyte containing 3 wt % sonicated Co3O4 nanoparticles (PVVA-3) delivers the highest ionic conductivity (4.62 × 10-3 S cm-1) of the series. This property is accompanied by a 51% enhancement in the apparent diffusion coefficient of triiodide versus both unmodified and unsonicated electrolyte samples. The dye-sensitized solar cell based on PVVA-3 displays a power conversion efficiency of 6.46% under AM1.5 G, 100 mW cm-2. By identifying the optimal loading of sonochemically processed nanoparticles, we are able to generate a homogenous extended particle network that effectively mobilizes redox-active species through a highly amorphous host matrix. This effect is manifested in a selective 51% enhancement in photocurrent density (JSC = 16.2 mA cm-2) and a lowered barrier to N719 dye regeneration (RCT = 193 Ω) versus an unmodified solar cell. To the best of our knowledge, this work represents the highest known efficiency to date for dye-sensitized solar cells based on a sonicated Co3O4-modified gel polymer electrolyte. Sonochemical processing, when applied in this manner, has the potential to make meaningful contributions toward the ongoing mission to achieve the widespread exploitation of stable and low-cost dye-sensitized solar cells.
We used an innovative approach involving hot pressing, low energy consumption, and no adhesive to transform bamboo biomass into a natural sustainable fiber-based biocomposite for structural and furniture applications. Analyses showed strong internal bonding through mechanical "nail-like" nano substances, hydrogen, and ester and ether bonds. The biocomposite encompasses a 10-fold increase in internal bonding strength with improved water resistance, fire safety, and environmentally friendly properties as compared to existing furniture materials using hazardous formaldehyde-based adhesives. As compared to natural bamboo material, this new biocomposite has improved fire and water resistance, while there is no need for toxic adhesives (mostly made from formaldehyde-based resin), which eases the concern of harmful formaldehyde-based VOC emission and ensures better indoor air quality. This surpasses existing structural and furniture materials made by synthetic adhesives. Interestingly, our approach can 100% convert discarded bamboo biomass into this biocomposite, which represents a potentially cost reduction alternative with high revenue. The underlying fragment riveting and cell collapse binding are obviously a new technology approach that offers an economically and sustainable high-performance biocomposite that provides solutions to structural and furniture materials bound with synthetic adhesives.
Immobilization can be used to improve the stability of lipases and enhances lipase recovery and reusability, which increases its commercial value and industrial applications. Nevertheless, immobilization frequently causes conformational changes of the lipases, which decrease lipase catalytic activity. in the present work, we synthesized UIO-66 and grafted UIO-66 crystals with proline for immobilization of Candida rugosa lipase (CRL). As indicated by steady-state fluorescence microscopy, grafting of proline onto UIO-66 crystals induced beneficial conformational change in CRL. CRL immobilized on UIO-66/Pro (CRL@UIO-66/Pro) demonstrated higher enzyme activity and better recyclability than that immobilized on UIO-66 (CRL@UIO-66) in both hydrolysis (CRL@UIO-66/Pro: 0.34 U; CRL@UIO-66: 0.15 U) and transesterification (CRL@UIO-66/Pro: 0.93 U; CRL@UIO-66: 0.25 U) reactions. The higher values of kcat and kcat/Km of CRL@UIO-66/Pro also showed that it had better catalytic efficiency as compared to CRL@UIO-66. It is also worth noting that CRL@UIO-66/Pro (0.93 U) demonstrated a much higher transesterification activity as compared to free CRL (0.11 U), indicating that UIO-66/Pro has increased the solvent stability of CRL. Both CRL@UIO-66 and CRL@UIO-66/Pro were also used for the fabrication of biosensors for nitrofen with a wide linear range (0-100 μM), lower limit of detection, and good recovery rate.
Hydrocarbon-fueled solid oxide fuel cells (SOFCs) that can operate in the intermediate temperature range of 500-700 °C represent an attractive SOFC device for combined heat and power applications in the industrial market. One of the ways to realize such a device relies upon exploiting an in situ steam reforming process in the anode catalyzed by an anti-carbon coking catalyst. Here, we report a new Ni and Ru bimetal-doped perovskite catalyst, Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.9Ni0.05Ru0.05O3-δ (BZCYYbNRu), with enhanced catalytic hydrogen production activity on n-butane (C4H10), which can resist carbon coking over extended operation durations. Ru in the perovskite lattice inhibits Ni precipitation from perovskite, and the high water adsorption capacity of proton conducting perovskite improves the coking resistance of BZCYYbNRu. When BZCYYbNRu is used as a steam reforming catalyst layer on a Ni-YSZ-supported anode, the single fuel cell not only achieves a higher power density of 1113 mW cm-2 at 700 °C under a 10 mL min-1 C4H10 continuous feed stream at a steam to carbon (H2O/C) ratio of 0.5 but also shows a much better operational stability for 100 h at 600 °C compared with those reported in the literature.
An abundant, highly active, and durable oxygen evolution reaction (OER) electrocatalyst is an enabling component for a more sustainable energy future. We report, herein, a molybdenum and niobium codoped B-site-ordered double perovskite oxide with a compositional formula of Ba2CoMo0.5Nb0.5O6-δ (BCMN) as an active and robust catalyst for OER in an alkaline electrolyte. BCMN displayed a low overpotential of 445 mA at a current density of 10 mA cm-2disk. BCMN also showed long-term stability in an alkaline medium. This work hints toward the possibility of combining a codoping approach with double perovskite structure formation to achieve significant enhancement in the OER performance.
Perovskite oxide is an attractive low-cost alternative catalyst for oxygen evolution reaction (OER) relative to the precious metal oxide-based electrocatalysts (IrO2 and RuO2). In this work, a series of Sr-doped La-based perovskite oxide catalysts with compositions of La1- xSr xFeO3-δ ( x = 0, 0.2, 0.5, 0.8, and 1) are synthesized and characterized. The OER-specific activities in alkaline solution increase in the order of LaFeO3-δ (LF), La0.8Sr0.2FeO3-δ (LSF-0.2), La0.5Sr0.5FeO3-δ (LSF-0.5), SrFeO3-δ (SF), and La0.2Sr0.8FeO3-δ (LSF-0.8). We establish a direct correlation between the enhancement in the specific activity and the amount of surface oxygen vacancies as well as the surface Fe oxidation states. The improved specific activity for LSF-0.8 is clearly linked to the optimum amount of surface oxygen vacancies and surface Fe oxidation states. We also find that the OER performance stability is a function of the crystal structure and the deviation in the surface La and/or Sr composition(s) from their bulk stoichiometric compositions. The cubic structure and lower deviation, as is the case for LSF-0.8, led to a higher OER performance stability. These surface performance relations provide a promising guideline for constructing efficient water oxidation.
Sodium ion batteries (SIBs) are considered one of the most promising alternatives for large-scale energy storage due largely to the abundance and low cost of sodium. However, the lack of high-performance cathode materials at low cost represents a major obstacle toward broad commercialization of SIB technology. In this work, we report a green route strategy that allows cost-effective fabrication of carbon-coated Na2FePO4F cathode for SIBs. By using vitamin C as a green organic carbon source and environmentally friendly water-based polyacrylic latex as the binder, we have demonstrated that the Na2FePO4F phase in the as-derived Na2FePO4F/C electrode shows a high reversible capacity of 117 mAh g-1 at a cycling rate of 0.1 C. More attractively, excellent rate capability is achieved while retaining outstanding cycling stability (∼85% capacity retention after 1000 charge-discharge cycles at a rate of 4 C). Further, in operando X-ray diffraction has been used to probe the evolution of phase structures during the charge-discharge process, confirming the structural robustness of the Na2FePO4F/C cathode (even when charged to 4.5 V). Accordingly, the poor initial Coulombic efficiency of some anode materials may be compensated by extracting more sodium ions from Na2FePO4F/C cathode at higher potentials (up to 4.5 V).
Here, we explore the use of two- and three-dimensional scaffolds of multiwalled-carbon nanotubes (MWNTs) for hepatocyte cell culture. Our objective is to study the use of these scaffolds in liver tissue engineering and drug discovery. In our experiments, primary rat hepatocytes, the parenchymal (main functional) cell type in the liver, were cultured on aligned nanogrooved MWNT sheets, MWNT yarns, or standard 2-dimensional culture conditions as a control. We find comparable cell viability between all three culture conditions but enhanced production of the hepatocyte-specific marker albumin for cells cultured on MWNTs. The basal activity of two clinically relevant cytochrome P450 enzymes, CYP1A2 and CYP3A4, are similar on all substrates, but we find enhanced induction of CYP1A2 for cells on the MWNT sheets. Our data thus supports the use of these substrates for applications including tissue engineering and enhancing liver-specific functions, as well as in in vitro model systems with enhanced predictive capability in drug discovery and development.
This paper reports the utilization of ZnO nanorod arrays (NRAs) doped with various concentrations of Ga (0, 0.5, 1, 2, and 3 at %) as electron acceptors in organic solar cells. The donor, poly(3-hexylthiophene) (P3HT), was spin coated onto Ga-doped ZnO NRAs that were grown on fluorine-doped tin oxide (FTO) substrates, followed by the deposition of a Ag electrode by a magnetron sputtering method. Adjusting the Ga precursor concentration allowed for the control of the structural and optical properties of ZnO NRAs. The short circuit current density increased with increasing Ga concentration from 0 to 1 at %, mainly because of improved exciton dissociation and increased charge extraction. Meanwhile, the reduced charge recombination and lower hole leakage current led to an increase in the open circuit voltage with Ga concentrations up to 1 at %. The device with the optimum Ga concentration of 1 at % exhibited power conversion efficiency nearly three times higher compared to the device without Ga doping. This finding suggests that the incorporation of Ga can be a simple and effective approach to improve the photovoltaic performance of organic solar cells.
Dye-sensitized solar cells (DSSCs) based on a donor-acceptor-donor oligothienylene dye containing benzothiadiazole (T4BTD-A) were cosensitized with dyes containing cis-configured squaraine rings (HSQ3 and HSQ4). The cosensitized dyes showed incident monochromatic photon-to-current conversion efficiency (IPCE) greater than 70% in the 300-850 nm wavelength region. The individual overall conversion efficiencies of the sensitizers T4BTD-A, HSQ3, and HSQ4 were 6.4%, 4.8%, and 5.8%, respectively. Improved power conversion efficiencies of 7.0% and 7.7% were observed when T4BTD-A was cosensitized with HSQ3 and HSQ4, respectively, thanks to a significant increase in current density (JSC) for the cosensitized DSSCs. Intensity-modulated photovoltage spectroscopy results showed a longer lifetime for cosensitized T4BTD-A+HSQ3 and T4BTD-A+HSQ4 compared to that of HSQ3 and HSQ4, respectively.