A data driven oil spill mapping using GMM clustering and damping ratio on X-Press Pearl ship disaster in the Indian Ocean.

The work presented in this paper is focused on the largest marine disaster to have occurred in the Indian Ocean due to the breakup of the container tanker ship X-Press Pearl. In order to identify the oil spill and its temporal evolution, a recently proposed damping ratio (DR) index is employed. To derive the DR, a data-driven GMM-EM clustering method optimized by stochastic ordering of the resulting classes in Sentinel 1 SAR time series imagery is proposed. A ship-born oil spill site is essentially considered to consist of three subsites: oil, open sea, and ship. The initial site probability densities were determined by using k-means clustering. In addition to the clustering method, two histogram-based approaches, namely contextual peak thresholding (CPT) and contextual peak ordering (CPO), were also formulated and presented. The improved histogram peak detection methods take into account spatial and contextual dependencies. The similarity of the marginal probability densities of the open sea and the oil classes makes it difficult to quantify the DR values to show the level of dampening. In the study, we show that reasonable class separability to correctly determine the σVV0,seaθ is possible by using GMM clustering. Resulting class separability's are also reported using JM and ML distances. The methods tested show the range of derived DR values stays significantly within similar ranges to each other. The outcomes were tested with the ground-based surveys conducted during the disaster for oil spill sites and other chemical compounds. The proposed methods are simple to execute, robust, and fully automated. Further, they do not require masking the oil or the selection of high-confidence water pixels manually.

Trap-Induced Long-Lived Internal Charge Separation in Sn-Doped MAPbBr3 Perovskite Films.

Sn-doped lead halide perovskites (LHPs) have attracted considerable attention for their lower bandgap and lower toxicity. While it is well-established that Sn doping easily introduces a lot of structural defects into LHP films, the extent to which these defects impact carrier dynamics has yet to be fully elucidated. Herein, we take Sn-doped MAPbBr3 films as an example to explore the influence of Sn doping on their carrier dynamics. The results show that Sn doping can simultaneously introduce many fillable electron traps and unfillable hole traps, consequently instigating an ultrafast carrier capture process. This further elicits long-lived internal charge separation between band edge and trap states or between two kinds of trap states, thereby enabling these carriers to persist for up to ∼2.6 µs. Our findings suggest that Sn doping potentially serves as an effective strategy to prolong the carrier lifetime in LHPs, which could pave the way for potential applications within Sn-based perovskites.

Time-Resolved Spectroscopy for Dynamic Investigation of Photoresponsive Metal-Organic Frameworks.

Photoresponsive MOFs with precise and adjustable reticular structures are attractive for light conversion applications. Uncovering the photoinduced carrier dynamics lays the essential foundation for the further development and optimization of the MOF material. With the application of time-resolved spectroscopy, photophysical processes including excimer formation, energy transfer/migration, and charge transfer/separation have been widely investigated. However, the identification of distinct photophysical processes in real experimental MOF spectra still remains difficult due to the spectral and dynamic complexity of MOFs. In this Perspective, we summarize the typical spectral features of these photophysical processes and the related analysis methods for dynamic studies performed by time-resolved photoluminescence (TR-PL) and transient absorption (TA) spectroscopy. Based on the recent understanding of excited-state properties of photoresponsive MOFs and the discussion of challenges and future outlooks, this Perspective aims to provide convenience for MOF kinetic analysis and contribute to the further development of photoresponsive MOF material.

Electron injection and defect passivation for high-efficiency mesoporous perovskite solar cells.

Printable mesoscopic perovskite solar cells (p-MPSCs) do not require the added hole-transport layer needed in traditional p-n junctions but have also exhibited lower power conversion efficiencies of about 19%. We performed device simulation and carrier dynamics analysis to design a p-MPSC with mesoporous layers of semiconducting titanium dioxide, insulating zirconium dioxide, and conducting carbon infiltrated with perovskite that enabled three-dimensional injection of photoexcited electrons into titanium dioxide for collection at a transparent conductor layer. Holes underwent long-distance diffusion toward the carbon back electrode, and this carrier separation reduced recombination at the back contact. Nonradiative recombination at the bulk titanium dioxide/perovskite interface was reduced by ammonium phosphate modification. The resulting p-MPSCs achieved a power conversion efficiency of 22.2% and maintained 97% of their initial efficiency after 750 hours of maximum power point tracking at 55 ± 5°C.

Printable Block Molecular Assemblies with Controlled Exciton Dynamics.

Creating hierarchical molecular block heterostructures, with the control over size, shape, optical, and electronic properties of each nanostructured building block can help develop functional applications, such as information storage, nanowire spectrometry, and photonic computing. However, achieving precise control over the position of molecular assemblies, and the dynamics of excitons in each block, remains a challenge. In the present work, the first fabrication of molecular heterostructures with the control of exciton dynamics in each block, is demonstrated. Additionally, these heterostructures are printable and can be precisely positioned using Direct Ink Writing-based (DIW) 3D printing technique, resulting in programable patterns. Singlet excitons with emission lifetimes on nanosecond or microsecond timescales and triplet excitons with emission lifetimes on millisecond timescales appear simultaneously in different building blocks, with an efficient energy transfer process in the heterojunction. These organic materials also exhibit stimuli-responsive emission by changing the power or wavelength of the excitation laser. Potential applications of these organic heterostructures in integrated photonics, where the versatility of fluorescence, phosphorescence, efficient energy transfer, printability, and stimulus sensitivity co-exist in a single nanowire, are foreseen.

Tunable Band Engineering Management on Perovskite MAPbBr3 /COFs Nano-Heterostructures for Efficient S-S Coupling Reactions.

Efficient artificial photosynthesis of disulfide bonds holds promises to facilitate reverse decoding of genetic codes and deciphering the secrets of protein multilevel folding, as well as the development of life science and advanced functional materials. However, the incumbent synthesis strategies encounter separation challenges arising from leaving groups in the ─S─S─ coupling reaction. In this study, according to the reaction mechanism of free-radical-triggered ─S─S─ coupling, light-driven heterojunction functional photocatalysts are tailored and constructed, enabling them to efficiently generate free radicals and trigger the coupling reaction. Specifically, perovskites and covalent organic frameworks (COFs) are screened out as target materials due to their superior light-harvesting and photoelectronic properties, as well as flexible and tunable band structure. The in situ assembled Z-scheme heterojunction MAPB-M-COF (MAPbBr3 = MAPB, MA+ = CH3 NH2 + ) demonstrates a perfect trade-off between quantum efficiency and redox chemical potential via band engineering management. The MAPB-M-COF achieves a 100% ─S─S─ coupling yield with a record photoquantum efficiency of 11.50% and outstanding cycling stability, rivaling all the incumbent similar reaction systems. It highlights the effectiveness and superiority of application-oriented band engineering management in designing efficient multifunctional photocatalysts. This study demonstrates a concept-to-proof research methodology for the development of various integrated heterojunction semiconductors for light-driven chemical reaction and energy conversion.

Artificial Photosynthetic System with Spatial Dual Reduction Site Enabling Enhanced Solar Hydrogen Production.

Although S-scheme artificial photosynthesis shows promise for photocatalytic hydrogen production, traditional methods often overly concentrate on a single reduction site. This limitation results in inadequate redox capability and inefficient charge separation, which hampers the efficiency of the photocatalytic hydrogen evolution reaction. To overcome this limitation, a double S-scheme system is proposed that leverages dual reduction sites, thereby preserving energetic photo-electrons and holes to enhance apparent quantum efficiency. The design features a double S-scheme junction consisting of CdS nanospheres decorated with anatase TiO2 nanoparticles coupled with graphitic C3 N4 . The as-prepared catalyst exhibits a hydrogen evolution rate of 26.84 mmol g-1  h-1 and an apparent quantum efficiency of 40.2% at 365 nm. This enhanced photocatalytic hydrogen evolution is ascribed to the efficient charge separation and transport induced by the double S-scheme. Both theoretical calculations and comprehensive spectroscopy tests (both in situ and ex situ) affirm the efficient charge transport across the catalyst interface. Moreover, substituting the reduction-type catalyst CdS with other similar sulfides like ZnIn2 S4 , ZnS, MoS2 and In2 S3 further confirms the feasibility of the proposed double S-scheme configuration. The findings provide a pathway to designing more effective double S-scheme artificial photosynthetic systems, opening up fresh perspectives in enhancing photocatalytic hydrogen evolution performance.

Diffusion-Controlled Crystal Engineering with Diverse Antisolvent Intervention for the Preparation of High-Quality Hybrid Perovskite Films.

Antisolvent engineering is routinely used to modulate the crystallization of perovskite films as they can offer an additional driving force for nucleation. Actually, the intervention of antisolvent into nucleation is thought to involve some relatively fast and complex processes, which, however, are not fully understood so far. Here, the diffusion of the organic amine cation FA+ (one dominated precursor) and its distribution in a spin-coating process in different antisolvents is simulated by the computational fluid dynamics (CFD) model. It is suggested that a moderate diffusion rate (like that in the case of toluene as an antisolvent) not only enables to form a very uniform distribution of FA+ ions on the substrate, beneficial to the uniform nucleation of the intermediate phase, but also can balance the nucleation and growth rates of the intermediate phase, thereby suppressing undesired heterogeneous nucleation and growth. Results show that the perovskite film fabricated using toluene as an antisolvent has a high quality, based on which higher power conversion efficiencies of up to 24.32% are achieved for perovskite solar cells.

Field-Induced Transport Anisotropy in Single-Crystalline All-Inorganic Lead-Halide Perovskite Nanowires.

The dynamic crystal lattice of halide perovskites facilitates the coupled transport of ions and electrons, offering innovative concepts in semiconductor iontronic devices that surpass solar cell applications. However, a comprehensive understanding of the intricacies of coupled ionic and electronic transport at the microscale remains ambiguous, owing to the inhomogeneity in ploy-crystalline perovskite thin films. In this work, we employed one-dimensional (1D) single-crystalline CsPbBr3 nanowires (NWs) to investigate the electric field induced ionic transport. Upon poling by an external bias, the previously uniform NW exhibits highly anisotropic ionic transport, which is identified as the origin of the giant switchable photovoltaic effect by spatially resolved scanning photocurrent microscopy. The subsequent ultrafast scanning photoluminescence (PL) microscopy measurements demonstrate significant localization of photocarriers near one terminal of the device, which is attributed to the accumulation of halogen vacancies. In addition, thanks to the enhancement of the local electric field, the poled device shows a 10-fold increase of photoresponse speed. Our findings favor the scale-down of perovskite devices to the submicrometer scale, extending their applications in self-powered iontronic and optoelectronic devices.

Implementation of laser flash photolysis for radical-induced reactions and environmental implications.

Confronted with the imperative crisis of water quality deterioration, the pursuit of state-of-the-art decontamination technologies for a sustainable future never stops. Fitting into the framework of suitability, advanced oxidation processes have been demonstrated as powerful technologies to produce highly reactive radicals for the degradation of toxic and refractory contaminants. Therefore, investigations on their radical-induced degradation have been the subject of scientistic and engineering interests for decades. To better understand the transient nature of these radical species and rapid degradation processes, laser flash photolysis (LFP) has been considered as a viable and powerful technique due to its high temporal resolution and rapid response. Although a number of studies exploited LFP for one (or one class of) specific reaction(s), reactions of many possible contaminants with radicals are largely unknown. Therefore, there is a pressing need to critically review its implementation for kinetic quantification and mechanism elucidation. Within this context, we introduce the development process and milestones of LFP with emphasis on compositions and operation principles. We then compare the specificity and suitability of different spectral modes for monitoring radicals and their decay kinetics. Radicals with high environmental relevance, namely hydroxyl radical, sulfate radical, and reactive chlorine species, are selected, and we discuss their generation, detection, and implications within the frame of LFP. Finally, we highlight remaining challenges and future perspectives. This review aims to advance our understandings of the implementation of LFP in radical-induced transient processes, and yield new insights for extrapolating this pump-probe technique to make significant strides in environmental implications.

Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero-Dimensional [(C6 H5 )4 P]2 SbCl5 Enabled by Pressure-Induced Lone Pair-π Interaction.

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6 H5 )4 P]2 SbCl5 . In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb3+ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected "bridge" for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic-inorganic hybrid systems.

Insight into the Key Restriction of BiVO4 Photoanodes Prepared by Pyrolysis Method for Scalable Preparation.

Bismuth Vanadate (BiVO4 ) photoanode has been popularly investigated for promising solar water oxidation, but its intrinsic performance has been greatly retarded by the direct pyrolysis method. Here we insight the key restriction of BiVO4 prepared by metal-organic decomposition (MOD) method. It is found that the evaporation of vanadium during the pyrolysis tends to cause a substantial phase impurity, and the unexpected few tetragonal phase inhibits the charge separation evidently. Consequently, suitably excessive vanadium precursor was adopted to eliminate the phase impurity, based on which the obtained intrinsic BiVO4 photoanode could exhibit photocurrent density of 4.2 mA cm-2 at 1.23 VRHE under AM 1.5 G irradiation, as comparable to the one fabricated by the currently popular two-step electrodeposition method. Furthermore, the excellent performance can be maintained on the enlarged photoanode (25 cm2 ), demonstrating the advantage of MOD method in scalable preparation. Our work provides new insight and highlights the glorious future of MOD method for the design of scale-up efficient BiVO4 photoanode.

Morphology-Dependent Carrier Accumulation Dynamics in Mixed Halide Perovskite Thin Films Caused by Phase Segregation.

The phase segregation in mixed halide perovskites is recently found to improve the photoluminescence quantum yield (PLQY) of the perovskites by concentrating the carriers. However, how phase segregation affects the photoinduced carrier dynamics is unclear. Herein, we find that the phase segregation in CH3NH3PbBrxI3-x mixed halide perovskite thin film is morphology-dependent by showing I-rich domains mainly along the grain boundaries. Ultrafast transient absorption (TA) and photoluminescence upconversion (PL-UC) spectroscopy measurements uncover that the carrier accumulation in the low energy I-rich domains includes two carrier transfer pathways. Carrier transfer from the Br-rich domain and the mixed phase to the I-rich domain is realized by consecutive hole (∼0.5 ps) and electron (<12.4 ps) transfer and energy transfer (<12.4 ps), respectively. The finding reveals the carrier funneling dynamic mechanism in phase-segregated halide perovskite films and provides a guideline for the applications of mixed halide perovskites in color-conversion devices or high-efficiency LEDs.

A Twin S-Scheme Artificial Photosynthetic System with Self-Assembled Heterojunctions Yields Superior Photocatalytic Hydrogen Evolution Rate.

Designing heterojunction photocatalysts imitating natural photosynthetic systems has been a promising approach for photocatalytic hydrogen generation. However, in the traditional Z-Scheme artificial photosynthetic systems, the poor charge separation, and rapid recombination of photogenerated carriers remain a huge bottleneck. To rationally design S-Scheme (i.e., Step scheme) heterojunctions by avoiding the futile charge transport routes is therefore seen as an attractive approach to achieving high hydrogen evolution rates. Herein, a twin S-scheme heterojunction is proposed involving graphitic C3 N4 nanosheets self-assembled with hydrogen-doped rutile TiO2 nanorods and anatase TiO2 nanoparticles. This catalyst shows an excellent photocatalytic hydrogen evolution rate of 62.37 mmol g-1 h-1 and high apparent quantum efficiency of 45.9% at 365 nm. The significant enhancement of photocatalytic performance is attributed to the efficient charge separation and transfer induced by the unique twin S-scheme structure. The charge transfer route in the twin S-scheme is confirmed by in situ X-ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) spin-trapping tests. Femtosecond transient absorption (fs-TA) spectroscopy, transient-state surface photovoltage (TPV), and other ex situ characterizations further corroborate the efficient charge transport across the catalyst interface. This work offers a new perspective on constructing artificial photosynthetic systems with S-scheme heterojunctions to enhance photocatalytic performance.

Probing longitudinal carrier transport in perovskite thin films via modified transient reflection spectroscopy.

Accurate characterization of the longitudinal (along the thickness direction) carrier transport property is of significant importance for evaluating the quality and performance of perovskite thin films. Herein, we report the development of a modified transient reflection (TR) spectroscopy method to realize the direct observation and determination of the longitudinal carrier transport process in MAPbI3 polycrystalline thin films. Unlike the traditional TR spectroscopy, the carrier transport dynamics along the film thickness is resolved by making the pump (excitation) and probe beams spatially separated on each side of the film, so that the carrier transport from the excitation side to the probe side is directly captured. Utilizing this method, the longitudinal carrier diffusion coefficients (D) in various perovskite films with different thicknesses and grain sizes (extracted from SEM images) are determined, showing D values of ∼1.5 to 1.8 cm2 s-1 (∼0.5 to 0.8 cm2 s-1) for films with grain size larger (smaller) than the thickness. This empirical correlation between the longitudinal D and film thickness/grain size provides a reference for quick quality screening and evaluation of perovskite polycrystalline thin films.

Imaging the Moisture-Induced Degradation Process of 2D Organolead Halide Perovskites.

Two-dimensional (2D) and quasi-2D Ruddlesden-Popper (RP) phase organolead halide perovskites are promising materials for both photovoltaic and optoelectronic devices. Although they are known to be more stable when exposed to moisture than their 3D counterpart, chemical degradation of these materials under moisture, which not only leads to a significant drop in device performance but also leads to lead leakage, yet remains one of the most serious hurdles for their practical applications. To gain insight into the degradation mechanism of 2D/quasi-2D perovskites under moisture conditions, the degradation pathway of 2D/quasi-2D (PEA)2(MA) n-1PbnI3n+1 (PEA = C6H5C2H4NH3 +, MA = CH3NH3 +, and n is the number of perovskite layers between adjacent organic spacer layers) perovskite single crystals (SCs) and thin film are explored. We observe the degradation process by mapping the photoluminescence of the 2D perovskites and demonstrate that the larger-n phases all directly degrade into the relative stable n = 1 phase and MAI and PbI2, which is a mechanism different from that in previous reports and further confirmed in the 2D perovskite thin film. This degradation process is also found to be independent of the boundary and morphology of the SCs. This discovery provides a new perspective for understanding the chemical degradation of the 2D perovskite materials and may inspire new solutions for improving their moisture stability.

Elucidating the Unique Hot Carrier Cooling in Two-Dimensional Inorganic Halide Perovskites: The Role of Out-of-Plane Carrier-Phonon Coupling.

Two-dimensional (2D) halide perovskites represent the natural semiconductor quantum wells (QWs), which hold great promise for optoelectronics. However, due to the hybrid structure of Ruddlesden-Popper 2D perovskites, the intrinsic nature of hot-carrier kinetics remains shielded within. Herein, we adopt CsPbBr3 nanoplates as a model system to reveal the intrinsic carrier dynamics in inorganic perovskite QWs. Interestingly, we revealed an ultrafast and hot-phonon-bottleneck (HPB)-free carrier cooling in monodisperse CsPbBr3 QWs, which is in sharp contrast to the bulk and nanocrystalline perovskites. The absence of HPB was attributed to the efficient out-of-plane triplet-exciton-LO-phonon coupling in 2D perovskites because of the structural anisotropy. Accordingly, the HPB can be activated by shutting down the out-of-plane energy loss route through forming the layer-stacked perovskite superlattice. The controllable on and off of HPB may provide new possibilities in optoelectronic devices and these findings deepen the understanding of a hot-carrier cooling mechanism in 2D perovskites.

Water-Stable Nickel Metal-Organic Framework Nanobelts for Cocatalyst-Free Photocatalytic Water Splitting to Produce Hydrogen.

Development of water-stable metal-organic frameworks (MOFs) for promising visible-light-driven photocatalytic water splitting is highly desirable but still challenging. Here we report a novel p-type nickel-based MOF single crystal (Ni-TBAPy-SC) and its exfoliated nanobelts (Ni-TBAPy-NB) that can bear a wide range of pH environment in aqueous solution. Both experimental and theoretical results indicate a feasible electron transfer from the H4TBAPy ligand (light-harvesting center) to the Ni-O cluster node (catalytic center), on which water splitting to produce hydrogen can be efficiently driven free of cocatalyst. Compared to the single crystal, the exfoliated two-dimensional (2D) nanobelts show more efficient charge separation due to its shortened charge transfer distance and remarkably enhanced active surface areas, resulting in 164 times of promoted water reduction activity. The optimal H2 evolution rate on the nanobelt reaches 98 µmol h-1 (ca. 5 mmol h-1 g-1) showing benchmarked apparent quantum efficiency (AQE) of 8.0% at 420 nm among water-stable MOFs photocatalysts.

Ultrafast and High-Yield Polaronic Exciton Dissociation in Two-Dimensional Perovskites.

Layered two-dimensional (2D) lead halide perovskites are a class of quantum well (QW) materials, holding dramatic potentials for optical and optoelectronic applications. However, the thermally activated exciton dissociation into free carriers in 2D perovskites, a key property that determines their optoelectronic performance, was predicted to be weak due to large exciton binding energy (Eb, about 100-400 meV). Herein, in contrast to the theoretical prediction, we discover an ultrafast (<1.4 ps) and highly efficient (>80%) internal exciton dissociation in (PEA)2(MA)n-1PbnI3n+1 (PEA = C6H5C2H4NH3+, MA = CH3NH3+, n = 2-4) 2D perovskites despite the large Eb. We demonstrate that the exciton dissociation activity in 2D perovskites is significantly promoted because of the formation of exciton-polarons with considerably reduced exciton binding energy (down to a few tens of millielectronvolts) by the polaronic screening effect. This ultrafast and high-yield exciton dissociation limits the photoluminescence of 2D perovskites but on the other hand well explains their exceptional performance in photovoltaic devices. The finding should represent a common exciton property in the 2D hybrid perovskite family and provide a guideline for their rational applications in light emitting and photovoltaics.

Oncolytic viruses for triple negative breast cancer and beyond.

Biological therapy is considered an alternative treatment capable of eliciting the same effects on tumors as surgery, radiotherapy, and chemotherapy. As a major player in biological therapy, oncolytic viruses (OVs) have attracted great attention and achieved good results. Specifically, the successful application of OVs in head and neck cancer, as well as melanoma, promoted its research in triple negative breast cancer (TNBC). TNBC is a high-risk molecular type of breast cancer, characterized by strong invasion, easy recurrence, and metastasis. Due to the absence of estrogen and progesterone receptors, as well as the absence of overexpression or gene amplification of human epidermal growth factor receptor 2 (HER2), endocrine therapy and anti HER-2 targeted therapy have proven ineffective. Although chemotherapy has shown substantial efficacy in some TNBC patients, the occurrence of drug resistance and poor prognosis have prompted the exploration of new and effective treatment methods. The emerging concept of OVs provides a new platform to treat TNBC. Indeed, several studies have confirmed the therapeutic effects of OVs in TNBC. Numerous studies have also investigated the efficacy of OVs in other malignances, including solid tumor clinical trials, thus further demonstrating the promising application of oncolytic virotherapy for TNBC. The primary focus of the current review is the examination of OV mechanisms underlying their antitumor properties, while also summarizing the ongoing progress in OV research regarding TNBC treatment, as well as the various combinatorial strategies comprising OVs and other therapies. We also briefly introduce specific relevant clinical trials and discuss some of the progress in the research of novel OVs for the treatment of other malignancies, thereby affirming the significant therapeutic potential of OVs for the treatment of TNBC, as well as other cancers.