Photocatalytic degradation of different types of microplastics by TiOx/ZnO tetrapod photocatalysts.

We investigated the use of titania coated ZnO tetrapods for photocatalytic degradation of two common types of microplastics, namely polyethylene (PE) microparticles and polyester (PES) microfibers. We found that the plastics morphology affects the rate of degradation, and that the use of electron scavengers is needed to maintain the reactivity of the photocatalysts over a prolonged period of time. Complete mass loss of PE and PES is achieved under UV illumination for 480 h and 624 h, respectively. In addition to pristine microplastics, the degradation of environmental microplastics sample (consisting primarily of polypropylene) was also demonstrated, though in this case longer degradation time (∼816 h) was needed to achieve complete mass loss of the samples.

Effect of Passivating Molecules and Antisolvents on Lifetime of Green Dion-Jacobson Perovskite Light-Emitting Diodes.

We investigated the influence of two passivating molecules containing a P═O group on the performance of quasi-2D Dion-Jacobson halide perovskite light-emitting diodes, namely, triphenylphosphine oxide (TPPO) and diphenyl-4-triphenylsilylphenyl phosphine oxide (TSPO1). We found that both passivating molecules lead to increased efficiency compared to control devices, while they had opposite effects on device lifetime, with a decrease observed for TPPO and an increase observed for TSPO1. The two passivating molecules resulted in differences in energy-level alignment, electron injection, film morphology and crystallinity, and ion migration during operation. While TPPO resulted in improved photoluminescence decay times, overall higher maximum external quantum efficiency (EQE) and device lifetime were obtained for TSPO1 compared to TPPO (14.4% vs 12.4% EQE, 341 min vs 42 min T50).

Iron-Based Oxygen Scavengers on Mesoporous Silica Nanospheres.

Iron-based materials are among the most commonly used oxygen scavengers. Here, we investigated the mesoporous silica nanosphere (MSN)-supported iron-based scavengers, such as FeOx nanoparticles and different atomic layer deposition (ALD) coatings (FeOx and Fe). We found that the scavenger performance is a result of a complex interplay between available Brunauer-Emmett-Teller surface area and the scavenger composition, with the combination of infiltrated nanoparticles and Fe-ALD coating resulting in the best performance. When the glucose-based treatment of MSN is used to further enhance oxygen scavenging capacity, Fe-ALD coating yields the best performance, with a high oxygen adsorption capacity of 126.8 mL/g. ALD deposition of Fe represents a versatile method to introduce Fe-based oxygen scavengers onto different supports, and it can facilitate the integration of scavengers with different types of packaging, as the deposition can be performed at a low temperature of 150 °C.

Dual Surface Modifications of NiOx/Perovskite Interface for Enhancement of Device Stability.

Various phosphonic acid based self-assembled monolayers (SAMs) have been commonly used for interface modifications in inverted perovskite solar cells. This typically results in significant enhancement of the hole extraction and consequent increase in the power conversion efficiency. However, the surface coverage and packing density of SAM molecules can vary, depending on the chosen SAM material and underlying oxide layer. In addition, different SAM molecules have diverse effects on the interfacial energy level alignment and perovskite film growth, resulting in complex relationships between surface modification, efficiency, and lifetime. Here we show that ethanolamine surface modification combined with [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) results in significant improvement in device stability compared to devices with 2PACz modification only. The significantly smaller size of ethanolamine enables it to fill any gaps in 2PACz coverage and provide improved interfacial defect passivation, while its different chemical structure enables it to provide complementary effects to 2PACz passivation. Consequently, the perovskite films are more stable under illumination (slower photoinduced segregation), and the devices exhibit significant stability enhancement. Despite similar power conversion efficiencies (PCE) between 2PACz only and combined ethanolamine-2PACz modification (PCE of champion devices ∼21.6-22.0% for rigid and ∼20.2-21.0% for flexible devices), the T80 lifetime under simulated solar illumination in ambient is improved more than 15 times for both rigid and flexible devices.

Interactive effects of temperature and salinity on toxicity of zinc oxide nanoparticles towards the marine mussel Xenostrobus securis.

Growing application of zinc oxide nanoparticles (ZnO-NPs) in global market has led to the concern over their potential environmental impacts. Filter feeders like mussels are prone to nanoparticles due to their superior filter-feeding ability. Temperature and salinity of coastal and estuarine seawaters often vary seasonally and spatially, and their changes may jointly influence physicochemical properties of ZnO-NPs and thus their toxicity. This study, therefore, aimed to investigate the interactive effect of temperatures (15, 25 and 30 °C) and salinities (12 and 32 PSU) on physicochemical properties and sublethal toxicity of ZnO-NPs towards a marine mussel Xenostrobus securis, and to compare that with the toxicity caused by Zn2+ ions (zinc sulphate heptahydrate). The results revealed increased particle agglomeration but decreased zinc ion release of ZnO-NPs at the highest temperature and salinity condition (30 °C and 32 PSU). After exposure, ZnO-NPs significantly reduced survival, byssal attachment rate and filtration rate of the mussels at high temperature and salinity (30 °C and 32 PSU). Glutathione S-transferase and superoxide dismutase activities in the mussels were suppressed at 30 °C. These aligned with the augmented zinc accumulation with increasing temperature and salinity which could likely be attributable to increased particle agglomeration of ZnO-NP and enhanced intrinsic filtration rate of the mussels under these conditions. Together with the observed lower toxic potency of Zn2+ compared to ZnO-NPs, our results suggested that the mussels might accumulate more zinc through particle filtration under higher temperature and salinity, eventually resulting in elevated toxicity of ZnO-NPs. Overall, this study demonstrated the necessity to consider the interactive effect of environmental factors such as temperature and salinity during the toxicity assessment of nanoparticles.

Contrasting toxicity of polystyrene nanoplastics to the rotifer Brachionus koreanus in the presence of zinc oxide nanoparticles and zinc ions.

Emerging contaminants such as nanoplastics and nanoparticles likely experience similar environmental behaviours, fate and effects but our knowledge of their combined toxicity is scanty. This study, therefore, investigated the joint toxicity of polystyrene nanoplastics (PNPs) and zinc oxide nanoparticles (ZnO-NPs) to an ecologically important rotifer Brachionus koreanus, and compared with the joint toxicity of PNPs and Zn ions (Zn-IONs from ZnSO4·7H2O). With increasing concentration, ZnO-NPs formed significant agglomeration with PNPs for up to 1.3 times of the original hydrodynamic size of ZnO-NPs, alongside doubling in their sedimentation and thereby losing 58% of their released Zn ions. In contrast, the availability of Zn-IONs was less affected by the agglomeration and sedimentation of PNPs, with only a loss of 18% of Zn ions at the highest concentration of PNPs. Consequently, as suggested by Concentration Addition and Independent Action models and the Model Deviation Ratios, ZnO-NPs and PNPs exerted an antagonistic interaction whereas Zn-IONs and PNPs exhibited an additive effect. We also advocate the use of the Nonparametric Response Surface method, which is more useful to predict the toxicity of chemical mixtures with interacting effects. Our findings suggested a potential difference between particle-particle and particle-ion interactions, especially at higher test concentrations, which may eventually affect their toxicity. We, therefore, call for a more systematic evaluation of commonly coexisting chemical mixtures which consist of nanoplastics and manufactured nanomaterials.

Encapsulation and Stability Testing of Perovskite Solar Cells for Real Life Applications.

With the progress in the development of perovskite solar cells, increased efforts have been devoted to enhancing their stability. With more devices being able to survive harsher stability testing conditions, such as damp heat or outdoor testing, there is increased interest in encapsulation techniques suitable for this type of tests, since both device architecture compatible with increased stability and effective encapsulation are necessary for those testing conditions. A variety of encapsulation techniques and materials have been reported to date for devices with different architectures and tested under different conditions. In this Perspective, we will discuss important factors affecting the encapsulation effectiveness and focus on the devices, which have been subjected to outdoor testing or damp heat testing. In addition to encapsulation requirements for these testing conditions, we will also discuss device requirements. Finally, we discuss possible methods for accelerating the testing of encapsulation and device stability and discuss the future outlook and important issues, which need to be addressed for further advancement of the stability of perovskite solar cells.

Hydrophobic Surface Coating Can Reduce Toxicity of Zinc Oxide Nanoparticles to the Marine Copepod Tigriopus japonicus.

Coated zinc oxide nanoparticles (ZnO-NPs) are more commonly applied in commercial products but current risk assessments mostly focus on bare ZnO-NPs. To investigate the impacts of surface coatings, this study examined acute and chronic toxicities of six chemicals, including bare ZnO-NPs, ZnO-NPs with three silane coatings of different hydrophobicity, zinc oxide bulk particles (ZnO-BKs), and zinc ions (Zn-IONs), toward a marine copepod, Tigriopus japonicus. In acute tests, bare ZnO-NPs and hydrophobic ZnO-NPs were less toxic than hydrophilic ZnO-NPs. Analyses of the copepod's antioxidant gene expression suggested that such differences were governed by hydrodynamic size and ion dissolution of the particles, which affected zinc bioaccumulation in copepods. Conversely, all test particles, except the least toxic hydrophobic ZnO-NPs, shared similar chronic toxicity as Zn-IONs because they mostly dissolved into zinc ions at low test concentrations. The metadata analysis, together with our test results, further suggested that the toxicity of coated metal-associated nanoparticles could be predicted by the hydrophobicity and density of their surface coatings. This study evidenced the influence of surface coatings on the physicochemical properties, toxicity, and toxic mechanisms of ZnO-NPs and provided insights into the toxicity prediction of coated nanoparticles from their coating properties to improve their future risk assessment and management.

Interfacial stabilization for inverted perovskite solar cells with long-term stability.

Perovskite solar cells (PSCs) commonly exhibit significant performance degradation due to ion migration through the top charge transport layer and ultimately metal electrode corrosion. Here, we demonstrate an interfacial management strategy using a boron chloride subphthalocyanine (Cl6SubPc)/fullerene electron-transport layer, which not only passivates the interfacial defects in the perovskite, but also suppresses halide diffusion as evidenced by multiple techniques, including visual element mapping by electron energy loss spectroscopy. As a result, we obtain inverted PSCs with an efficiency of 22.0% (21.3% certified), shelf life of 7000 h, T80 of 816 h under damp heat stress (compared to less than 20 h without Cl6SubPc), and initial performance retention of 98% after 2000 h at 80 °C in inert environment, 90% after 2034 h of illumination and maximum power point tracking in ambient for encapsulated devices and 95% after 1272 h outdoor testing ISOS-O-1. Our strategy and results pave a new way to move PSCs forward to their potential commercialization solidly.

Unraveling the Crystallization Kinetics of 2D Perovskites with Sandwich-Type Structure for High-Performance Photovoltaics.

2D perovskite solar cells with high stability and high efficiency have attracted significant attention. A systematical static and dynamic structure investigation is carried out to show the details of 2D morphology evolution. A dual additive approach is used, where the synergy between an alkali metal cation and a polar solvent leads to high-quality 2D perovskite films with sandwich-type structures and vertical phase segregation. Such novel structure can induce high-quality 2D slab growth and reduce internal and surface defects, resulting in a high device efficiency of 16.48% with enhanced continuous illumination stability and improved moisture (55-60%) and thermal (85 °C) tolerances. Transient absorption spectra reveal the carrier migration from low n to high n species with different kinetics. An [PbI6 ]4- octagon coalescence transformation mechanism coupled with metal and organic cations wrapped is proposed. By solvent vapor annealing, a recrystallization and reorientation of the 2D perovskite slabs occurs to form an ideal structure with improved device performance and stability.

In vivo toxicities of nine engineered nano metal oxides to the marine diatom Skeletonema costatum and rotifer Brachionus koreanus.

This study compared in vivo acute toxicities of nine engineered nano metal oxides to the marine diatom Skeletonema costatum and rotifer Brachionus koreanus. The sequence of their toxicities to S. costatum, based on growth inhibition, was: nano zinc oxide (nZnO) > nTiO2 (rutile) > nMgO > Annealed nMgO > nTiO2 (anatase) > Î³-nAl2O3 > nIn2O3 > α-nAl2O3 > nSnO2. Similarly, nZnO was also the most toxic to B. koreanus, but the other nano metal oxides were non-lethal. nMgO and nZnO were confirmed to trigger reactive oxygen species (ROS) mediated toxicity to the two marine organisms, while nTiO2 (both anatase and rutile forms) likely induced oxidative stress as shown by their acellular ROS production. nZnO may also cause damage in the endocrine system of B. koreanus, as indicated by the increased transcription of retinoid X receptor. Annealed nMgO reduces its toxicity via removal of O2- and impurities from its surface.

Side-Chain Engineering of Donor-Acceptor Conjugated Small Molecules As Dopant-Free Hole-Transport Materials for Efficient Normal Planar Perovskite Solar Cells.

Simultaneously improving efficiency and stability, which are particularly crucial factors for the commercialization of perovskite solar cells (PSCs), remains a major challenge. For high-efficiency normal PSCs, the development of stable dopant-free hole-transport materials (HTMs) seems imperative. Here, we developed potential donor-acceptor small molecules (BTTI) as HTMs for normal planar PSCs. Through tailoring its alkyl side-chain length as BTTI-C6, BTTI-C8, and BTTI-C12, our results show that upon shortening the side chain of BTTI, the hole mobility, film-forming capability, and resultant device performance were remarkably improved, with the device conversion efficiencies of 19.69% for BTTI-C6, 18.89% for BTTI-C8, and 17.49% for BTTI-C12. Meanwhile, compared to those made with the routine doped Spiro-OMeTAD, devices based on our dopant-free HTMs exhibited significantly improved stability. This work paves the way to the development of effective dopant-free HTMs for high-performance PSCs.

Dopant-Free Small-Molecule Hole-Transporting Material for Inverted Perovskite Solar Cells with Efficiency Exceeding 21.

Hole-transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long-term stability, high-performance dopant-free small-molecule HTMs (SM-HTMs) are greatly desired. However, such dopant-free SM-HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor-acceptor-type SM-HTMs (MPA-BTI and MPA-BTTI) are devised, which synergistically integrate several design principles for high-performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant-free MPA-BTTI-based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long-term stability under illumination, which breaks the long-time standing bottleneck in the development of dopant-free SM-HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well-aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA-BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high-performance dopant-free SM-HTMs in PVSCs.

Novel Molecular Doping Mechanism for n-Doping of SnO2 via Triphenylphosphine Oxide and Its Effect on Perovskite Solar Cells.

Molecular doping of inorganic semiconductors is a rising topic in the field of organic/inorganic hybrid electronics. However, it is difficult to find dopant molecules which simultaneously exhibit strong reducibility and stability in ambient atmosphere, which are needed for n-type doping of oxide semiconductors. Herein, successful n-type doping of SnO2 is demonstrated by a simple, air-robust, and cost-effective triphenylphosphine oxide molecule. Strikingly, it is discovered that electrons are transferred from the R3P+ O- σ-bond to the peripheral tin atoms other than the directly interacted ones at the surface. That means those electrons are delocalized. The course is verified by multi-photophysical characterizations. This doping effect accounts for the enhancement of conductivity and the decline of work function of SnO2 , which enlarges the built-in field from 0.01 to 0.07 eV and decreases the energy barrier from 0.55 to 0.39 eV at the SnO2 /perovskite interface enabling an increase in the conversion efficiency of perovskite solar cells from 19.01% to 20.69%.

A Cryogenic Process for Antisolvent-Free High-Performance Perovskite Solar Cells.

A cryogenic process is introduced to control the crystallization of perovskite layers, eliminating the need for the use of environmentally harmful antisolvents. This process enables decoupling of the nucleation and the crystallization phases by inhibiting chemical reactions in as-cast precursor films rapidly cooled down by immersion in liquid nitrogen. The cooling is followed by blow-drying with nitrogen gas, which induces uniform precipitation of precursors due to the supersaturation of precursors in the residual solvents at very low temperature, while at the same time enhancing the evaporation of the residual solvents and preventing the ordered precursors/perovskite from redissolving into the residual solvents. Using the proposed techniques, the crystallization process can be initiated after the formation of a uniform precursor seed layer. The process is generally applicable to improve the performance of solar cells using perovskite films with different compositions, as demonstrated on three different types of mixed halide perovskites. A champion power conversion efficiency (PCE) of 21.4% with open-circuit voltage (VOC ) = 1.14 V, short-circuit current density ( JSC ) = 23.5 mA cm-2 , and fill factor (FF) = 0.80 is achieved using the proposed cryogenic process.

Room-temperature single-photon emitters in titanium dioxide optical defects.

Fluorescence properties of crystallographic point defects within different morphologies of titanium dioxide were investigated. For the first time, room-temperature single-photon emission in titanium dioxide optical defects was discovered in thin films and commercial nanoparticles. Three-level defects were identified because the g(2) correlation data featured prominent shoulders around the antibunching dip. Stable and blinking photodynamics were observed for the single-photon emitters. These results reveal a new room-temperature single-photon source within a wide bandgap semiconductor.

Molecule-Doped Nickel Oxide: Verified Charge Transfer and Planar Inverted Mixed Cation Perovskite Solar Cell.

Both conductivity and mobility are essential to charge transfer by carrier transport layers (CTLs) in perovskite solar cells (PSCs). The defects derived from generally used ionic doping method lead to the degradation of carrier mobility and parasite recombinations. In this work, a novel molecular doping of NiOx hole transport layer (HTL) is realized successfully by 2,2'-(perfluoronaphthalene-2,6-diylidene)dimalononitrile (F6TCNNQ). Determined by X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy, the Fermi level (EF ) of NiOx HTLs is increased from -4.63 to -5.07 eV and valence band maximum (VBM)-EF declines from 0.58 to 0.29 eV after F6TCNNQ doping. The energy level offset between the VBMs of NiOx and perovskites declines from 0.18 to 0.04 eV. Combining with first-principle calculations, electrostatic force microscopy is applied for the first time to verify direct electron transfer from NiOx to F6TCNNQ. The average power conversion efficiency of CsFAMA mixed cation PSCs is boosted by ≈8% depending on F6TCNNQ-doped NiOx HTLs. Strikingly, the champion cell conversion efficiency of CsFAMA mixed cations and MAPbI3 -based devices gets to 20.86% and 19.75%, respectively. Different from passivation effect, the results offer an extremely promising molecular doping method for inorganic CTLs in PSCs. This methodology definitely paves a novel way to modulate the doping in hybrid electronics more than perovskite and organic solar cells.

Characterization of Low-Frequency Excess Noise in CH3NH3PbI3-Based Solar Cells Grown by Solution and Hybrid Chemical Vapor Deposition Techniques.

In this study, detailed investigations of low-frequency noise (LFN) characteristics of hybrid chemical vapor deposition (HCVD)- and solution-grown CH3NH3PbI3 (MAPI) solar cells are reported. It has been shown that LFN is a ubiquitous phenomenon observed in all semiconductor devices. It is the smallest signal that can be measured from the device; hence, systematic characterization of the LFN properties can be utilized as a highly sensitive nondestructive tool for the characterization of material defects in the device. It has been demonstrated that the noise power spectral densities of the devices are critically dependent on the parameters of the fabrication process, including the growth ambient of the perovskite layer and the incorporation of the mesoscopic structures in the devices. Our experimental results indicated that the LFN arises from a thermally activated trapping and detrapping process, resulting in the corresponding fluctuations in the conductance of the device. The results show that the presence of oxygen in the growth ambient of the HCVD process and the inclusion of an mp-TiO2 layer in the device structure are two important factors contributing to the substantial reduction in the density of the localized states in the MAPI devices. Furthermore, the lifetimes of the MAPI perovskite-based solar cells are strongly dependent on the material defect concentration. The degradation process is substantially more rapid for the devices with higher initial defect density compared to the devices prepared under optimized conditions and structure that exhibit substantially lower initial trap density.

Regulation of engineered nanomaterials: current challenges, insights and future directions.

Substantial production and wide applications of engineered nanomaterials (ENMs) have raised concerns over their potential influences on the environment and humans. However, regulations of products containing ENMs are scarce, even in countries with the greatest volume of ENMs produced, such as the United States and China. After a comprehensive review of life cycles of ENMs, five major challenges to regulators posed by ENMs are proposed in this review: (a) ENMs exhibit variable physicochemical characteristics, which makes them difficult for regulators to establish regulatory definition; (b) Due to diverse sources and transport pathways for ENMs, it is difficult to monitor or predict their fates in the environment; (c) There is a lack of reliable techniques for quantifying exposures to ENMs; (d) Because of diverse intrinsic properties of ENMs and dynamic environmental conditions, it is difficult to predict bioavailability of ENMs on wildlife and the environment; and (e) There are knowledge gaps in toxicity and toxic mechanisms of ENMs from which to predict their hazards. These challenges are all related to issues in conventional assessments of risks that regulators rely on. To address the fast-growing nanotechnology market with limited resources, four ENMs (nanoparticles of Ag, TiO2, ZnO and Fe2O3) have been prioritized for research. Compulsory reporting schemes (registration and labelling) for commercial products containing ENMs should be adopted. Moreover, to accommodate their potential risks in time, an integrative use of quantitative structure-activity relationship and adverse outcome pathway (QSAR-AOP), together with qualitative alternatives to conventional risk assessment are proposed as tools for decision making of regulators.

Lead removal from water - dependence on the form of carbon and surface functionalization.

We have investigated lead adsorption on different forms of nanostructured carbon, namely multiwall carbon nanotubes (MWCNT) and reduced graphene oxide (RGO) functionalized with different functional groups (hydroxyl, carboxyl, and amino groups). We found that the same functional group does not result in the same performance trends for different nanostructured carbons. Drastically different behavior was observed for the amino-group functionalization, where a significant improvement is observed for MWCNT, while worse performance compared to non-functionalized material is obtained for RGO. On the other hand, hydroxyl and carboxyl group functionalization improves the lead adsorption regardless of the form of carbon. The best performing RGO sample, namely carboxyl group functionalized one, exhibited maximum lead adsorption capacity of 298.49 mg g-1 which was significantly higher than that of the best performing MWCNT sample (amino-functionalized MWCNT, 58.547 mg g-1).