Transition metals-based electrocatalysts on super-flat substrate for perovskite photovoltaic hydrogen production with 13.75% solar to hydrogen efficiency.

Harnessing the inexhaustible solar energy for water splitting is regarded one of the most promising strategies for hydrogen production. However, sluggish kinetics of oxygen evolution reaction (OER) and expensive photovoltaics have hindered commercial viability. Here, an adhesive-free electrodeposition process is developed for in-situ preparation of earth-abundant electrocatalysts on super-flat indium tin oxide (ITO) substrate. NiFe hydroxide exhibited prominent OER performance, achieving an ultra-low overpotential of 236 mV at 10 mA/cm2 in alkaline solution. With the superior OER activity, we achieved an unassisted solar water splitting by series connected perovskite solar cells (PSCs) of 2 cm2 aperture area with NiFe/ITO//Pt electrodes, yielding overall solar to hydrogen (STH) efficiency of 13.75 %. Furthermore, we upscaled the monolithic facility to utilize perovskite solar module for large-scale hydrogen production and maintained an approximate operating current of 20 mA. This creative strategy contributes to the decrease of industrial manufacturing expenses for perovskite-based photovoltaic-electrochemical (PV-EC) hydrogen production, further accelerating the conversion and utilization of carbon-free energy.

Tether-entangled conjugated helices.

A new design concept, tether-entangled conjugated helices (TECHs), is introduced for helical polyaromatic molecules. TECHs consist of a linear polyaromatic ladder backbone and periodically entangling tethers with the same planar chirality. By limiting the length of tether, all tethers synchronously bend and twist the backbone with the same manner, and change it into a helical ribbon with a determinate helical chirality. The 3D helical features are customizable via modular synthesis by using two types of synthons, the planar chiral tethering unit (C 2 symmetry) and the docking unit (C 2h symmetry), and no post chiral resolution is needed. Moreover, TECHs possess persistent chiral properties due to the covalent locking of helical configuration by tethers. Concave-type and convex-type oligomeric TECHs are prepared as a proof-of-concept. Unconventional double-helix π-dimers are observed in the single crystals of concave-type TECHs. Theoretical studies indicate the smaller binding energies in double-helix π-dimers than conventional planar π-dimers. A concentration-depend emission is found for concave-type TECHs, probably due to the formation of double-helix π-dimers in the excited state. All TECHs show strong circularly polarized luminescence (CPL) with dissymmetric factors (|g lum|) generally over 10-3. Among them, the (P)-T4-tBu shows the highest |g lum| of 1.0 × 10-2 and a high CPL brightness of 316 M-1 cm-1.

Cation reactivity inhibits perovskite degradation in efficient and stable solar modules.

Perovskite solar modules (PSMs) show outstanding power conversion efficiencies (PCEs), but long-term operational stability remains problematic. We show that incorporating N,N-dimethylmethyleneiminium chloride into the perovskite precursor solution formed dimethylammonium cation and that previously unobserved methyl tetrahydrotriazinium ([MTTZ]+) cation effectively improved perovskite film. The in situ formation of [MTTZ]+ cation increased the formation energy of iodine vacancies and enhanced the migration energy barrier of iodide and cesium ions, which suppressed nonradiative recombination, thermal decomposition, and phase segregation processes. The optimized PSMs achieved a record (certified) PCE of 23.2% with an aperture area of 27.2 cm2, with a stabilized PCE of 23.0%. The encapsulated PSM retained 87.0% of its initial PCE after ~1900 hours of maximum power point tracking at 85°C and 85% relative humidity under 1.0-sun illumination.

Dynamic dissipative control for fuzzy distributed parameter cyber physical system under input quantization and DoS attack.

This article explores the dissipative control for a class of nonlinear DP-CPS (distributed parameter cyber physical system) within a finite-time interval. By utilizing a Takagi-Sugeno (T-S) fuzzy model to represent the system's nonlinear aspects, the studied system is formulated as a class of fuzzy parabolic partial differential equation (PDE). In order to optimize network resources, both the system state and input signal are subjected to quantization using dynamic quantizers. Subsequently, a dynamic state control strategy is proposed, taking into account potential DoS attack. The finite-time boundedness of the fuzzy parabolic PDE is analyzed, with respect to the influence of quantization, through the construction of an appropriate Lyapunov functional. The article then presents the conditions for finite-time dissipative control design, alongside the adjustment parameters for the dynamic quantizers within the fuzzy closed-loop system. Furthermore, the decoupling of interlinked nonlinear terms in the control design conditions is achieved by using an arbitrary matrix. Finally, an example is provided and the simulation results indicate the effectiveness of the dissipative control method proposed.

Inhibiting Ion Migration and Stabilizing Crystal-Phase in Halide Perovskite via Directly Incorporated Fluoride Anion.

Fluoride anion (F-) with extremely high electronegativity has been under intensive investigation in perovskite solar cells due to its remarkable defect suppression and great improvement of device performance. Nevertheless, these researches only focus on the surface, grain boundaries, or interface modification, the direct insertion of F- into the crystal lattice of regular lead halide perovskite films is still unrevealed. Herein, F- was successfully incorporated into the perovskite lattice by overcoming the insolubility of PbF2 via the introduced pyridinium halide as a novel volatile solubilizing ligand. The strong electronegativity of F- can strongly increase the binding energy of all the ions in CsPbI2Br and inhibit their defect formations. A trace amount of F- incorporation not only enhanced the optoelectronic properties but also effectively mitigated the ion migration and phase separation simultaneously. The photovoltaic performance and operational stability of perovskite solar cells were significantly improved with a champion efficiency of 17.78 % (38.01 %) under AM 1.5G (1000 lux indoor light). Moreover, F- can also be directly inserted into the hybrid perovskite lattice and greatly stabilized crystal-phase, enabling efficient fully MA-free FAPbI3 devices with 25.10 % efficiency. Our strategy sheds light on F-containing perovskites and provides a promising way to tackle ion migration and stabilize the crystal phase in halide perovskites.

High-Efficiency Perovskite Solar Cells with Improved Interfacial Charge Extraction by Bridging Molecules.

The interface between the perovskite layer and electron transporting layer is a critical determinate for the performance and stability of perovskite solar cells (PSCs). The heterogeneity of the interface critically affects the carrier dynamics at the buried interface. To address this, a bridging molecule, (2-aminoethyl)phosphonic acid (AEP), is introduced for the modification of SnO2/perovskite buried interface in n-i-p structure PSCs. The phosphonic acid group strongly bonds to the SnO2 surface, effectively suppressing the surface carrier traps and leakage current, and uniforming the surface potential. Meanwhile, the amino group influences the growth of perovskite film, resulting in higher crystallinity, phase purity, and fewer defects. Furthermore, the bridging molecules facilitate the charge extraction at the interface, as indicated by the femtosecond transient reflection (fs-TR) spectroscopy, leading to champion power conversion efficiency (PCE) of 26.40% (certified 25.98%) for PSCs. Additionally, the strengthened interface enables improved operational durability of ≈1400 h for the unencapsulated PSCs under ISOS-L-1I protocol.

Proteasome inhibitors FHND6091 enhance the ability of NK cells to kill tumor cells through multiple mechanisms.

The immune system has a strong connection to tumors. When a tumor cell is recognized as an abnormal cell by the immune system, the immune system may initiate an immune response to kill the tumor cell. In this study, RNA sequencing was performed on multiple myeloma (MM) cells treated with the proteasome inhibitor FHND6091. The transcriptional changes induced by FHND6091 in RPMI8226 cells aligned notably with immune response activation and results indicated upregulation of cGAS-STING pathway-related genes in the FHND6091-treated group. In vivo and in vitro experiments had demonstrated that FHND6091 stimulated the immunoreaction of MM cells via activation of the cyclic guanosine monophosphate-adenosine synthase/stimulator of interferon genes (cGAS-STING) pathway. This activation resulted in the generation of type-I interferons and the mobilization of natural killer (NK) cells. Notably, FHND6091 upregulated the levels of calreticulin and the protein ligands UL16-binding protein 2/5/6, MHC class I chain-related A (MICA), and MICB on the surface of MM cells. Subsequently, upon engaging with the surface activation receptors of NK cells, these ligands triggered NK cell activation, leading to the subsequent elimination of tumor cells. Thus, our findings elucidated the mechanism whereby FHND6091 exerted its immunotherapeutic activity as a STING agonist, enhancing the killing ability of NK cells against tumor cells.

The Development of Quinoxaline-Based Electron Acceptors for High Performance Organic Solar Cells.

In the recent advances of organic solar cells (OSCs), quinoxaline (Qx)-based nonfullerene acceptors (QxNFAs) have attracted lots of attention and enabled the recorded power conversion efficiency approaching 20%. As an excellent electron-withdrawing unit, Qx possesses advantages of many modifiable sites, wide absorption range, low reorganization energy, and so on. To develop promising QxNFAs to further enhance the photovoltaic performance of OSCs, it is necessary to systematically summarize the QxNFAs reported so far. In this review, all the focused QxNFAs are classified into five categories as following: SM-Qx, YQx, fused-YQx, giant-YQx, and polymer-Qx according to the molecular skeletons. The molecular design concepts, relationships between the molecular structure and optoelectronic properties, intrinsic mechanisms of device performance are discussed in detail. At the end, the advantages of this kind of materials are summed up, the molecular develop direction is prospected, the challenges faced by QxNFAs are given, and constructive solutions to the existing problems are advised. Overall, this review presents unique viewpoints to conquer the challenge of QxNFAs and thus boost OSCs development further toward commercial applications.

Tethered Helical Ladder-Type Aromatic Lactams.

Tethered nonplanar aromatics (TNAs) make up an important class of nonplanar aromatic compounds showing unique features. However, the knowledge on the synthesis, structures, and properties of TNAs remains insufficient. In this work, a new type of TNAs, the tethered aromatic lactams, is synthesized via Pd-catalyzed consecutive intramolecular direct arylations. These molecules possess a helical ladder-type conjugated system of up to 13 fused rings. The overall yields ranged from 3.4 to 4.3%. The largest of the tethered aromatic lactams, 6L-Bu-C14, demonstrates a guest-adaptive hosting capability of TNAs for the first time. When binding fullerene guests, the cavity of 6L-Bu-C14 became more circular to better accommodate spherical fullerene molecules. The host-guest interaction is thoroughly studied by X-ray crystallography, theoretical calculations, fluorescence titration, and nuclear magnetic resonance (NMR) titration experiments. 6L-Bu-C14 shows stronger binding with C70 than with C60 due to the better convex-concave π-π interaction. P and M enantiomers of all tethered aromatic lactams show distinct and persistent chiroptical properties and demonstrate the potential of chiral TNAs as circularly polarized luminescence (CPL) emitters.

Polydentate Ligand Reinforced Chelating to Stabilize Buried Interface toward High-Performance Perovskite Solar Cells.

The instability of the buried interface poses a serious challenge for commercializing perovskite photovoltaic technology. Herein, we report a polydentate ligand reinforced chelating strategy to strengthen the stability of buried interface by managing interfacial defects and stress. The bis(2,2,2-trifluoroethyl) (methoxycarbonylmethyl)phosphonate (BTP) is employed to manipulate the buried interface. The C=O, P=O and two -CF3 functional groups in BTP synergistically passivate the defects from the surface of SnO2 and the bottom surface of the perovskite layer. Moreover, The BTP modification contributes to mitigated interfacial residual tensile stress, promoted perovskite crystallization, and reduced interfacial energy barrier. The multidentate ligand modulation strategy is appropriate for different perovskite compositions. Due to much reduced nonradiative recombination and heightened interface contact, the device with BTP yields a promising power conversion efficiency (PCE) of 24.63 %, which is one of the highest efficiencies ever reported for devices fabricated in the air environment. The unencapsulated BTP-modified devices degrade to 98.6 % and 84.2 % of their initial PCE values after over 3000 h of aging in the ambient environment and after 1728 h of thermal stress, respectively. This work provides insights into strengthening the stability of the buried interface by engineering multidentate chelating ligand molecules.

Optimizing the Buried Interface in Flexible Perovskite Solar Cells to Achieve Over 24% Efficiency and Long-Term Stability.

The buried interface of the perovskite layer has a profound influence on its film morphology, defect formation, and aging resistance from the outset, therefore, significantly affects the film quality and device performance of derived perovskite solar cells. Especially for FAPbI3 , although it has excellent optoelectronic properties, the spontaneous transition from the black perovskite phase to nonperovskite phase tends to start from the buried interface at the early stage of film formation then further propagate to degrade the whole perovskite. In this work, by introducing ─NH3 + rich proline hydrochloride (PF) with a conjugated rigid structure as a versatile medium for buried interface, it not only provides a solid α-phase FAPbI3 template, but also prevents the phase transition induced degradation. PF also acts as an effective interfacial stress reliever to enhance both efficiency and stability of flexible solar cells. Consequently, a champion efficiency of 24.61% (certified 23.51%) can be achieved, which is the highest efficiency among all reported values for flexible perovskite solar cells. Besides, devices demonstrate excellent shelf-life/light soaking stability (advanced level of ISOS stability protocols) and mechanical stability.

Asymmetric Π-Bridge Engineering Enables High-Permittivity Benzo[1,2-B:4,5-b']Difuran-Conjugated Polymer for Efficient Organic Solar Cells.

Organic solar cells (OSCs) exhibit complex charge dynamics, which are closely correlated with the dielectric constant (ɛr ) of photovoltaic materials. In this work, a series of novel conjugated copolymers based on benzo[1,2-b:4,5-b']difuran (BDF) and benzotriazole (BTz) is designed and synthesized, which differ by the nature of π-bridge from one another. The PBDF-TF-BTz with asymmetric furan and thiophene π-bridge demonstrates a larger ɛr of 4.22 than PBDF-dT-BTz with symmetric thiophene π-bridge (3.15) and PBDF-dF-BTz with symmetric furan π-bridge (3.90). The PBDF-TF-BTz also offers more favorable molecular packing and appropriate miscibility with non-fullerene acceptor Y6 than its counterparts. The corresponding PBDF-TF-BTz:Y6 OSCs display efficient exciton dissociation, fast charge transport and collection, and reduced charge recombination, eventually leading to a power conversion efficiency of 17.01%. When introducing a fullerene derivative (PCBO-12) as a third component, the PBDF-TF-BTz:Y6:PCBO-12 OSCs yield a remarkable FF of 80.11% with a high efficiency of 18.10%, the highest value among all reported BDF-polymer-based OSCs. This work provides an effective approach to developing high-permittivity photovoltaic materials, showcasing PBDF-TF-BTz as a promising polymer donor for constructing high-performance OSCs.

Defect Compensation and Lattice Stabilization Enables High Voltage Output in Tin Halide Perovskite Solar Cells.

Tin halide perovskite solar cells (PSCs) are regarded as the most promising lead-free alternatives for photovoltaic applications. However, they still suffer from uncompetitive photovoltaic performance because of the facile Sn2+ oxidation and Sn-related defects. Herein, a defect and carrier management strategy by using diaminopyridine (DP) and 4-bromo-2,6-diaminopyridine (4BrDP) as multifunctional additives for tin halide perovskites is reported. Both DP and 4BrDP induced strong interaction with tin perovskites by coordinate bonding and N─H···I hydrogen bonding, which greatly suppresses the micro-strain and Urbach energy of tin halide perovskite films. The strong hydrogen bonding inhibits the formation of I3 - and related defect density. Meanwhile, the electron-donor species of halogen bond in 4BrDP provides higher reactivity of 2 and 6 sites, which indicates stronger passivation ability with tin halide perovskites. These advances enable a champion power conversion efficiency (PCE) of 13.40% in 4BrDP-processed devices with remarkable improvement in both open-circuit voltage (Voc) of 881 mV and fill factor (FF) of 71.26%. The 4BrDP devices retain 91% and 82% of the pristine PCE after 2000 h storage in N2 atmosphere and 1000 h under 85 °C, respectively. Therefore, this work provides new insight into molecular design for high-performance and stable lead-free optoelectronics.

A Polarization-Sensitive Photodetector with Patterned CH3NH3PbCl3 Film.

Perovskite photodetectors with polarization-sensitive properties have gained significant attention due to their potential applications in fields such as imaging and remote sensing. Most perovskite photodetectors concentrate on iodine (I) or bromine (Br)-based materials, primarily due to their straightforward fabrication techniques. The utilization of chloride (Cl)-based perovskites with wider bandgaps, such as CH3NH3PbCl3, is relatively limited. In this work, polarized perovskite photodetectors are prepared by a patterned spatially confined method with polarization sensitivity and excellent optoelectronic properties. The patterned perovskite photodetectors (PP-PDs) not only exhibit outstanding photoelectric conversion performance but also demonstrate polarization sensitivity. PP-PDs showcase remarkable performance, including on/off ratios of 3.4 × 104, an extremely low dark current of 1.56 × 10-11 A, and a rapid response time of microseconds. The responsivity and detectivity of PP-PDs reach 10.6 A W-1 and 3 × 1012 Jones, respectively, positioning them as among the highest-performing MAPbCl3-based photodetectors reported to date. Furthermore, polarization layered imaging sensing is achieved using stepwise scanning of the device. This work provides innovative ideas for realizing high-performance polarized perovskite photodetectors.

Passivating Dipole Layer Bridged 3D/2D Perovskite Heterojunction for Highly Efficient and Stable p-i-n Solar Cells.

Constructing 3D/2D perovskite heterojunction is a promising approach to integrate the benefits of high efficiency and superior stability in perovskite solar cells (PSCs). However, in contrast to n-i-p architectural PSCs, the p-i-n PSCs with 3D/2D heterojunction have serious limitations in achieving high-performance as they suffer from a large energetic mismatch and electron extraction energy barrier from a 3D perovskite layer to a 2D perovskite layer, and serious nonradiative recombination at the heterojunction. Here a strategy of incorporating a thin passivating dipole layer (PDL) onto 3D perovskite and then depositing 2D perovskite without dissolving the underlying layer to form an efficient 3D/PDL/2D heterojunction is developed. It is revealed that PDL regulates the energy level alignment with the appearance of interfacial dipole and strongly interacts with 3D perovskite through covalent bonds, which eliminate the energetic mismatch, reduce the surface defects, suppress the nonradiative recombination, and thus accelerate the charge extraction at such electron-selective contact. As a result, it is reported that the 3D/PDL/2D junction p-i-n PSCs present a power conversion efficiency of 24.85% with robust stability, which is comparable to the state-of-the-art efficiency of the 3D/2D junction n-i-p devices.

Synergistic Modification for Efficient Perovskite Solar Cells with Small Voltage Loss.

The power conversion efficiency (PCE) of perovskite solar cells has improved quickly in the past few years, but the PCE is still much lower than the theoretical limit. The relatively high energy loss (Eloss) is one of the critical factors limiting the PCE. To resolve the above issues, a synergistic modification strategy was used herein to minimize Eloss. RbCl and potassium polyacrylate (K-PAM) were used to modify the SnO2 layer. Additionally, Pb(Ac)2 was introduced into PbI2 to further improve the film quality. The synergistic modification strategy reduced the defects in SnO2 and perovskite and improved the energy-level alignment, enabling significantly reduced Eloss and enhanced photovoltaic performance. The best PCE of 24.07% was achieved, which was much higher than that of the control device (20.86%). The Eloss was only 0.349 eV for the target device. Good stability was achieved for the cells made using modified SnO2 and perovskite layers.

Ionic Liquid-Induced Multisite Synergistic Interactions for Highly Efficient Inverted Perovskite Solar Cells.

The interfacial properties of p-i-n inverted perovskite solar cells (PSCs) play a key role in further improving the photovoltaic performance of PSCs. Herein, multisite synergistic interactions were constructed using ionic liquids (ILs) prepared by mixing urea and choline chloride (ChCl) to substantially improve the interfacial properties of inverted PSCs. Systematically theoretical calculations and experimental studies are comprehensively performed, which reveal that the C═O···Pb2+ coordination interaction, N-H···I hydrogen bond, and Cl-Pb bond could be simultaneously formed between the perovskites and IL, and Ch in IL could interact with the perovskite by occupying the formamidinium site. Meanwhile, -OH/π and -NH/π interactions could be formed between -OH and -NH in IL and the phenyl group in PTAA, respectively. These multisite synergistic interactions are beneficial to improve the perovskite film quality and interfacial properties of inverted PSCs, which could greatly suppress nonradiative recombination within the PSCs. Consequently, the inverted PSCs show an impressive efficiency of 22.4% and an excellent electroluminescence efficiency of 3.7%.

In Situ Cross-Linking Strategy to Enable Highly Stable Perovskite Solar Cells.

The perovskite solar cells (PSCs) have achieved great success in power conversion efficiency due to their excellent optoelectrical properties of perovskite. However, the instability of PSCs severely impedes their commercialization. Recently, in situ cross-linking strategy has been proposed to mitigate stability issues of PSCs, enabling highly efficient and stable PSCs. Here, the critical factors that lead to the degradation of PSCs are first outlined. Then, a comprehensive review of in situ cross-linking strategy in perovskite to enhance the moisture, thermal, illumination, and bending stress resistance properties of PSCs is presented. Furthermore, the detailed mechanism underlying these advantageous effects is discussed pertaining to crystallization regulation, immobilization of ions, water resistance, and release of unfavorable stress. Finally, the current challenges and further development trends of in situ cross-linking strategy in PSCs and extension to other optoelectronic devices are prospected.

Regulating the crystallization dynamics through hydrogen bonding for high efficiency tin halide perovskite solar cells.

Aniline was introduced into a solution of tin halide perovskite precursor to interact with formamidinium iodide (FAI) through hydrogen bonding, which optimized the crystal orientation of the tin halide perovskite and contributed to the charge transport and structural stabilization. The lead-free tin halide perovskite solar cells achieved a power conversion efficiency of 12.04% together with a high open-circuit voltage of 788 mV.

Diagnostic Value of Serum Creatinine and Cystatin-C-Based Indices and Ishii Score in Cancer-Related Sarcopenia.

BACKGROUND: Sarcopenia is a key factor affecting the prognosis of cancer patients; however, identifying patients at risk remains challenging. The serum creatinine/cystatin C ratio (CCR) and the sarcopenia index (SI) are new biomarkers for sarcopenia screening. The Ishii test score is an equation based on age, grip strength, and calf circumference for sarcopenia screening. However, their performances in advanced cancer patients have not been thoroughly studied. We aimed to evaluate and compare the accuracy of three screening tools in diagnosing cancer-related sarcopenia. METHODS: A total of 215 cancer patients with a median age of 60.5 y were enrolled in this cross-sectional study. The Asian Working Group for Sarcopenia 2019 (AWGS2019) criteria were used as a standard. The diagnostic accuracies of the CCR, SI, and Ishii screening test were analyzed in terms of sensitivity, specificity, negative and positive predictive values, the Youden index, and the receiver operating characteristic (ROC) curve. RESULTS: According to the AWGS2019 criteria, the prevalence of sarcopenia and severe sarcopenia was 47.9% and 18.6%, respectively. The CCR, SI (positively), and Ishii scores (negatively) were correlated with muscle mass. Accordingly, sarcopenia was negatively correlated with CCR and SI, while it was significantly positively correlated with the Ishii score. In males, the AUCs of the CCR, SI, and Ishii scores were 0.743 (95%CI 0.65-0.836), 0.758 (95%CI 0.665-0.852), and 0.833 (95%CI 0.751-0.909), respectively. In females, the AUCs of the CCR, SI, and Ishii scores were 0.714 (95%CI 0.61-0.818), 0.737 (95%CI 0.635-0.839), and 0.849 (95%CI 0.775-0.932), respectively. The AUC of the Ishii score was significantly higher than that of the other screening tools (p < 0.001). The cut-off value of the optimal Ishii score was 102.3 (sensitivity: 93.2%, specificity: 59.1%) for males and 98.3 (sensitivity: 93.3%, specificity: 64.7%) for females. CONCLUSIONS: The CCR and SI based on serum CysC and creatinine had a remarkably similar overall diagnostic accuracy for sarcopenia in advanced cancer. Among the above three sarcopenia screening tools, the Ishii score chart seemed to have better predictive values of sarcopenia in cancer patients.