http://onlinelibrary.wiley.com/rss/journal/10.1002/(ISSN)1521-4095

A recent article by Barnes and co-workers reported an experimental re-evaluation of earlier work on photoisomerization reactions inside optical cavities under conditions of strong light-matter coupling. They correctly highlight the importance of controlling irradiation conditions from sample to sample where optical cavities are involved. This comment aims to emphasize the great lengths the original study went to ensure exactly this.

Recently, an article by Barnes and co-workers reported an in-depth experimental re-evaluation of the earlier work on photoisomerization reactions inside optical cavities under conditions of strong light-matter coupling. That earlier work, which constituted the first demonstration of ‘polaritonic chemistry’, associated cavity-induced modifications of photoisomerization rates with the emergence of strong light-matter coupling (and the formation of polaritonic states). Barnes and co-workers instead found that cavity-induced changes in light absorption can account for changes in the photochemical reaction rates. While Barnes and co-workers correctly highlight the importance of controlling irradiation conditions from sample to sample where optical cavities are involved, this comment aims to emphasize the great length the original study went to ensure exactly this. The original experimental methods are summarized to point out the significant differences between them and those conducted by Barnes and co-workers. Furthermore, the importance of monochromatic photoexcitation at an isosbestic point rather than using broadband (UV through to IR) irradiation, as well as the careful control for photon flux reaching the molecular layer in all samples, as per the original work, is discussed. Further examination of important issues facing this new and developing domain of Physical Chemistry, is anticipated.

A time-division multiplexing physical unclonable function (TDM-PUF) label based on multicolor phosphorescent carbon dots (CDs) is proposed, which leverages the variations in wavelengths and lifetimes of the phosphorescent CDs to construct time-resolved multidimensional cryptographic protocols. This study provides a competitive anti-counterfeiting label and inspires the development of novel anti-counterfeiting strategies.

Phosphorescent materials offer a promising approach to information encryption due to their long luminescence lifetimes and high signal-to-noise ratios. However, fixed phosphorescent patterns are vulnerable to imitation over time, limiting their effectiveness in advanced encryption. Here, a time-division multiplexing physical unclonable function (TDM-PUF) label utilizing multicolor phosphorescent carbon dots (CDs) is proposed that leverages variations in wavelength and lifetime to construct time-resolved, multidimensional cryptographic protocols. Efficient multi-color phosphorescence in CDs is achieved by enhancing intersystem crossing, suppressing non-radiative transitions through confinement effects, and regulating emission spectra via energy transfer. The random spatial distribution and unpredictable emissions of phosphorescent CDs significantly enhance the complexity of the PUF system, thereby fortifying its defenses against mimicry attacks. Furthermore, this PUF system exhibits multiple optical responses over time, allowing correct information recognition only at specified time nodes, achieving time-resolved anti-counterfeiting. Finally, by segmenting PUF labels based on emission color and time channels, non-overlapping multicolor and multi-time segments are achieved, enabling highly secure time-division multiplexed encryption. The study provides a competitive anti-counterfeiting label and inspires the development of novel anti-counterfeiting strategies.

Understanding the complex interplay between local structure and physical properties is a key challenge in high entropy oxide (HEO) research, particularly concerning electronic transport. This work demonstrates the profound influence of local chemical inhomogeneity and underlying epitaxial strain on the electronic transport properties of HEO thin film with perovskite structure, paving pathways to tailor electronic properties in high-entropy regime.

Understanding the electronic transport properties of thin films of high-entropy oxide (HEO), having multiple elements at the same crystallographic site, is crucial for their potential electronic applications. However, very little is known about the metallic phase of HEOs even in bulk form. This work delves into the interplay between global and local structural distortion and electronic properties of single crystalline thin films of (La0.2Pr0.2Nd0.2Sm0.2Eu0.2)NiO3, which exhibit metal-insulator transition under tensile strain. Employing electron microscopy and elemental resolved electron energy loss spectroscopy, we provide direct evidence of nanoscale chemical inhomogeneities at the rare-earth site, leading to a broad distribution of Ni–O–Ni bond angles. However, the octahedral rotation pattern remains the same throughout. The metallic phase consists of insulating patches with more distorted Ni–O–Ni bond angles, responsible for higher resistance exponents with increased compositional complexity. Moreover, a rare, fully metallic state of HEO thin film is achieved under compressive strain. We further demonstrate a direct correlation between the suppression of the insulating behavior and increased electronic hopping. Our findings provide a foundation for exploring Mott-Anderson electron localization physics in the high-entropy regime.

A core-shell perovskite composite with a highly durable electrochemical activity for oxygen catalysis is developed as an air electrode for reversible protonic ceramic cells (RPCCs) via a unique solid-state reaction. This work also demonstrates a new pathway to developing highly durable air electrode materials for RPCCs technology, accelerating RPCCs’ commercialization.

Reversible protonic ceramic cells (RPCCs) offer a promising pathway to efficient and reversible energy conversion, accelerating the global shift to renewables. However, the RPCCs’ commercialization faces limitations in air electrode materials. Traditional cobalt-based perovskite air electrodes, while effective, suffer from high cost and environmental concerns. Alternative materials, such as SrFeO3-δ (SF)-based perovskites, offer potential, yet durability issues, including thermal-expansion mismatch and mechanical instability, hinder their practical application. Here, a unique solid-state reaction between SF and negative-thermal-expansion (NTE) material is demonstrated to yield a core-shell perovskite composite as a highly durable RPCCs air electrode. Specifically, by calcining a mixture of SF and an NTE material, ZrW2O8 (ZWO), the in situ incorporation of ZWO into the SF lattice is achieved, resulting in a non-closed core-shell composite, comprising single perovskite SraFebZrcWdO3-δ (SP-SFZW) core and B-site cation ordered double perovskite SrxFeyZrmWnO6-δ (DP-SFZW) shell. Both SP-SFZW and DP-SFZW serve as oxygen catalysts, while DP-SFZW shell additionally acts as a thermal expansion suppressor and mechanical support structure, effectively mitigating electrode cracking and delamination from other cell components during RPCC operation. Consequently, the composite electrode demonstrates comparable catalytic activity to SF, coupled with significantly enhanced durability. This work illustrates a novel approach for developing robust RPCCs air electrode.

An AEM-derived proton acceptor-electron donor mechanism is proposed in RuO2 by constructing an interstitial-substitutional mixed solid solution structure (C,Ta-RuO2), in which the interstitial C as the proton acceptor decreases the deprotonation energy barrier, while the substitutional Ta as the electron donor weakens the Ru─O bond covalency, thereby breaking the activity-stability trade-off of RuO2 in acidic OER.

The acidic oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane electrolyzer (PEMWE) often face a trade-off between activity and stability due to inherent linear relationship and overoxidation of metal atoms in highly oxidative environments, while following the conventional adsorbate evolution mechanism (AEM). Herein, a favorable AEM-derived proton acceptor-electron donor mechanism (PAEDM) is proposed in RuO2 by constructing interstitial-substitutional mixed solid solution structure (denoted as C,Ta-RuO2), which can effectively break the activity-stability trade-off of RuO2 in acidic OER. In situ spectroscopy experiments and theoretical calculations reveal that the interstitial C as the proton acceptor reduces the deprotonation energy barrier, enhancing catalytic activity, while the substitutional Ta as the electron donor donates electrons to the Ru sites via bridging oxygen, weakening the Ru─O bond covalency and preventing over-oxidation of surface Ru, thereby ensuring long-term stability. Under the guidance of this mechanism, the optimized C,Ta-RuO2 simultaneously achieves far low overpotential (η10 = 171 mV) and ultra-long stability (over 1300 h) for the acidic OER. More remarkably, a homemade PEMWE using C,Ta-RuO2 as the anode also shows high water splitting performance (1.63 V@1 A cm−2). This work supplies a novel strategy to guide future developments on efficient OER electrocatalysts toward water oxidation.

Breaking Quantum Confinement in Yb3⁺-Doped ZnSe QDs: Surface-energy engineering enables scalable growth beyond the exciton Bohr radius with high-purity blue emission (453 nm), narrow full width at half maximum (FWHM) of 46 nm, and exceptional photoluminescence quantum yield (PLQY) of 67.5%.

Large ZnSe quantum dots (QDs) with an emission peak ≈450 nm hold significant promise for display technologies. However, achieving efficient pure-blue emission through the enlargement of ZnSe nanocrystals remains a significant challenge. In this study, a breakthrough is reported in growing large-size ZnSe QDs well beyond the exciton Bohr radius through Yb3+ doping strategy. Yb3+ doping reduces the surface energy of the ZnSe (220) crystal plane and alleviates interface strain in the ZnSe/ZnS structure, enabling the QDs to grow larger while maintaining enhanced crystal stability. The resulting Yb: ZnSe/ZnS QDs exhibit pure-blue emission at 453 nm, with a full width at half maximum (FWHM) of 46 nm and a high photoluminescence quantum yield (PLQY) of 67.5%. When integrated into quantum dot light-emitting diodes (QLEDs), the devices display electroluminescence (EL) at 455 nm, with an external quantum efficiency (EQE) of 1.35%, and a maximum luminance of 1337.08 cd m−2.

A heterogeneous microgel–hydrogel hybrid is developed to construct a multiscale vascular network through embedded bioprinting and guided vascular morphogenesis. With a high density of hepatocytes, a bioengineered thick vascularized liver tissue model achieves a rapid and promising functional compensation in rats with 85% hepatectomy via direct vascular integration, providing a theraputi paradigm for physiological-related engineered tissue in animals with acute disease.

3D bioprinting of liver tissue with high cell density (HCD) shows great promise for restoring function in cases of acute liver failure, where a substantial number of functional cells are required to perform essential physiological tasks. Direct vascular anastomosis is critical for the successful implantation of these bioprinted vascularized tissues into the host vasculature, allowing for rapid functional compensation and addressing various acute conditions. However, conventional hydrogels used to encapsulate high-density cells often lack the mechanical properties needed to withstand the shear forces of physiological blood flow, often resulting in implantation failure. In this study, a heterogeneous microgel–hydrogel hybrid is developed to carry HCD hepatocytes and support the embedded bioprinting of hierarchical vascular structures. By optimizing the ratio of microgel to biomacromolecule, the covalently crosslinked network offers mechanical integrity and enables direct vascular anastomosis, ensuring efficient nutrient and oxygen exchange. The bioprinted thick, vascularized constructs, containing HCD hepatocytes, are successfully implanted in rats after 85% hepatectomy, leading to swift functional recovery and prolonged survival. This study presents a strategy to enhance regenerative therapy outcomes through advanced bioprinting and vascular integration techniques.

The α-FAPbI3 perovskite, ideal for high-efficiency solar cells, suffers from impurity phases causing defects and instability. Using FAI/MASCN vapors repairs impurities into α-FAPbI3, enhancing charge transport and morphology. This achieves 26.05% efficiency, with large-area devices (24.52% for 1 cm2, 22.35% for 17.1 cm2). Cyclic repair retains 94.3% efficiency after two cycles, significantly boosting device durability.

The photoactive α-phase of formamidinium lead iodide perovskite (α-FAPbI3) is regarded as one of the ideal materials for high-efficiency perovskite solar cells (PSCs) due to its superior optoelectronic properties. However, during the deposition of α-FAPbI3 perovskite films, the presence of impurity phases, such as PbI2 and δ-FAPbI3, can cause the formation of inherent defects, which leads to suboptimal charge transport and extraction properties, as well as inadequate long-term stability in the film's morphology and structure. To address these issues, an impurity phase repair strategy is employed using FAI/MASCN mixed vapors to convert the impurity phases into light-absorbing α-FAPbI3. Meanwhile, this recrystallization process also facilitates the recovery of its characteristic morphology, thereby improving efficiency and enhancing the durability of PSCs. This approach promotes the PSCs to obtain an efficiency of 26.05% (with a certified efficiency of 25.67%, and steady-state PCE of 25.41%). Additionally, this approach is suitable for the fabrication of large-area devices, obtaining a 1 cm2 device with a PCE of 24.52% and a mini-module (with an area of 17.1 cm2) with a PCE of 22.35%. Furthermore, it is found that this strategy enables cyclic repair of aged perovskite films, with the perovskite solar cells retaining ≈ 94.3% of their initial efficiency after two cycles of repair, significantly enhancing the lifetime of the perovskite solar cells.

A self-assembled interface orthogonal strategy is first applied to construct pseudo-planar heterojunction organic photovoltaics with controllable vertical gradient distribution morphology. Introducing low surface-energy N2200 to self-assemble molecular layer on PM6 surface overcomes erosion effect and modulates phase morphology, thus achieving the highest efficiency of 19.86% via air-printing process.

Precisely regulating vertically distributed morphology by blade-coating process is crucial to realize high-performance large-scale pseudo-planar heterojunction organic photovoltaics (OPVs). However, the thermodynamic motion and random diffusion of donor/acceptor (D/A) generated from the differences in surface energy and concentration during sequentially blade-coating process will cause great challenges for obtaining ideal active layer morphology. Herein, this study have proposed a self-assembled interface orthogonal strategy by introducing low surface energy guest (N2200) to form protective layer on PM6 surface, which counteracts erosion from orthogonal solution of acceptor to enhance continuity of D/A phases, thus promoting directional carrier migration and effectively suppressing energetic disorder. Finally, N2200-modified device achieves the highest power conversion efficiency (PCE) of 19.86%, and large-area module (16.94 cm2) exhibits exceptional PCE (16.43%). This investigation presents innovative insights into morphology issue triggered by molecular motion and provides an effective method for air-printing large-scale OPVs with precisely controlled morphology based on non-halogenated solvent.

A novel copper-sulfur-nitrogen cluster Cu8SN is synthesized by using a strong anchoring ability protective ligand (2-mercaptopyrimidine) and a relatively weak monodentate tert-butyl mercaptan ligand. Then, a precise thermal-resection strategy is applied to only peel the targeted weak ligands off, which induces a structural transformation of the initial Cu8SN cluster into a new and more stable Cu–S–N cluster (Cu8SN–T). Cu8SN–T exhibits greatly enhanced light-harvesting abilities and full-spectrum responsive overall CO2 photoreduction with ≈100% CO2-to-CO selectivity.

Atomically precise copper clusters are desirable as catalysts for elaborating the structure–activity relationships. The challenge, however, lies in their tendency to sinter when protective ligands are removed, resulting in the destruction of the structural integrity of the model system. Herein, a copper-sulfur-nitrogen cluster [Cu8(StBu)4(PymS)4] (denoted as Cu8SN) is synthesized by using a mixed ligand approach with strong chelating 2-mercaptopyrimidine (PymSH) ligands and relatively weak monodentate tert-butyl mercaptan ligands. A precise thermal-resection strategy is applied to selectively peel only the targeted weak ligands off, which induces a structural transformation of the initial Cu8 cluster into a new and more stable Cu–S–N cluster [Cu8(S)2(PymS)4] (denoted as Cu8SN-T). The residual bridging S2− within the metal core forms asymmetric Cu-S species with a near-infrared (NIR) response, which endows Cu8SN-T with the capability for full-spectrum responsive CO2 photoreduction, achieving a ≈100% CO2-to-CO selectivity. Especially for NIR-driven CO2 reduction, it has a CO evolution of 42.5 µmol g−1 under λ > 780 nm. Importantly, this work represents the first NIR light-responsive copper cluster for efficient CO2 photoreduction and opens an avenue for the precise manipulation of metal cluster structures via a novel thermolysis strategy to develop unprecedented functionalized metal cluster materials.

A chlorine-substituted aromatic polycyclic compound is introduced into perovskite solar cells to regulate perovskite crystallization, passivate various defects, and enhance hole transport at the HTL/perovskite interface. This approach achieved high efficiencies of 25.04% for 1 cm2 cells and 22.81% for 12 cm2 modules, with excellent stability (maintaining 80% of initial efficiency after 2500 h of MPP tracking under ISOS-L-1 standards).

Film morphology and surface/interface defect density play a critical role in determining the efficiency and stability of perovskite solar cells (PSCs). Here, a chlorine-substituted aromatic polycyclic derivative (BNCl) is reported, which shows strong interaction with both lead iodide and dimethyl sulfoxide, to regulate the crystallization of perovskite, along with effective passivation of grain boundaries and surface. In addition, the extruded BNCl molecule at the hole transport layer (HTL)/perovskite interface can facilitate the hole transport, leading to better charge transfer. As a result, certified power conversion efficiencies (PCEs) of 25.04% and 22.81% are achieved for PSCs and minimodules with aperture areas of 1 cm2 and 12 cm2 respectively. In addition, the device maintained 80% of its initial efficiency after 2500 h of maximum power point (MPP) tracking under ISOS-L-1 standard.

Centimeter-sized porous single-crystalline MoN monoliths with unsaturated Mo–N coordination structures are fabricated through solid-state phase transformation. The porous single-crystalline MoN integrates the structural features, suitable hydrogen adsorption energy, high electronic conductivity and intrinsic catalytic activity, demonstrating low Tafel slopes, minimal charge transfer resistances and long-term stability across all-pH conditions, significantly surpassing traditional Pt/C electrodes.

Platinum is widely used in the important components in most electrochemical energy conversion systems while as a noble metal it faces the inevitable challenge of limited reserves. Herein, porous single–crystalline (PSC) molybdenum nitride (MoN) monoliths are reported at the centimeter scale that surpass platinum for all–pH hydrogen evolution. Free–standing PSC MoN electrode with the pore size of ≈6 nm and porosity of ≈72% present both noble–metal–like electronic structure and unsaturated Mo─N coordination structures at surface, contributing to remarkably high intrinsic electrocatalytic activity. The unprecedented overpotentials of as low as 13 and 11 mV are presented at the geometrical current density of 10 mA cm−2 for hydrogen evolution in H2SO4 (pH 0) and KOH (pH 14) media, respectively, which is dramatically superior to commercial Pt electrodes. As a result of the structural stability, the outstanding long–term durability for all pH hydrogen evolution is demonstrated without visible degradation in a continuous operation for 300 h.

This review presents a strategic vision for integrating micro- and nanobots in the pipeline for infection diagnosis, prevention, and treatment. To develop these robots as a practical solution for infection management, their design principles are clarified based on their propulsion mechanisms and then categorized infection management domains based on usage scenarios.

Medical micro- and nano-bots (MMBs and MNBs) have attracted a lot of attention owing to their precise motion for accessing difficult-to-reach areas in the body. These emerging tools offer the promise of non-invasive diagnostics and therapeutics for a wide range of ailments. Here, it is highlighted how MMBs and MNBs can revolutionize infection management. The latest applications of MMBs and MNBs are explored for infection prevention, including their use as accurate, minimally invasive surgeons and diagnosis, where they function as sensitive and rapid biosensors or carriers for contrast agents for real-time imaging of infected tissue. Further, the applications are outlined in treatment serving as anti-biofilm agents and smart carriers for antibiotics and anti-infective biologics. The current challenges in designing MMBs and MNBs are highlighted for overcoming immune barriers, moving to deep infected tissue, and swimming in low Reynolds numbers and discuss mitigating strategies. Finally, as a future perspective, the potential advantages of multi-drive propulsion, bioinspired, and artificial-intelligence-trained MMBs and MNBs are discussed, with a special focus on challenges and opportunities for their commercialization.

Soft chemical intercalation of the van der Waals magnetic semiconductor CrSBr induces a quasi-1D charge density wave (CDW) phase. The combination of this CDW with ferromagnetism from a spin-polarized band generates an unusual coupling of the charge and spin modulations in the intercalated material.

In materials with 1D electronic bands, electron–electron interactions can produce intriguing quantum phenomena, including spin-charge separation and charge density waves (CDW). Most of these systems, however, are non-magnetic, motivating a search for anisotropic materials where the coupling of charge and spin may affect emergent quantum states. Here, chemical intercalation of the van der Waals magnetic semiconductor CrSBr yields Li0.17(2)(tetrahydrofuran)0.26(3)CrSBr, which possesses an electronically driven quasi-1D CDW with an onset temperature above room temperature. Concurrently, electron doping increases the magnetic ordering temperature from 132 to 200 K and switches its interlayer magnetic coupling from antiferromagnetic to ferromagnetic. The spin-polarized nature of the anisotropic bands that give rise to this CDW enforces an intrinsic coupling of charge and spin. The coexistence and interplay of ferromagnetism and charge modulation in this exfoliatable material provide a promising platform for studying tunable quantum phenomena across a range of temperatures and thicknesses.

High-performance 721 nm-excitable solid upconversion porous aromatic frameworks (UC PAFs) was constructed and applied to a broad-range oxygen sensing and efficient heterogeneous photoredox catalysis. Moreover, homogeneous triple exciton energy is recognized to facilitate exciton diffusion, resulting in a high upconversion quantum yield (1.5% with an upper limit of 50%).

The development of long-wavelength excitable solid upconversion materials and the regulation of exciton behavior is important for solar energy harvesting, photocatalysis, and other emerging applications. However, the approaches for regulating exciton diffusion are very limited, resulting in extremely poor photonic upconversion performance in solid-state. Here, the annihilation unit is integrated into porous aromatic frameworks (PAFs) and loaded with photosensitizer to construct efficient 721 nm-excitable solid upconversion material (upconversion quantum yield up to 1.5%, upper limit 50%). Most importantly, we found that the steric hindrance of annihilator units breaks the π-conjugation between the annihilation unit and the PAFs framework to form the homogeneous triplet exciton energy, which is conducive to the exciton diffusion. After increasing the exciton diffusion constant from 2.0 × 10−6 to 1.34 × 10−5 cm2 s−1, the upconversion quantum yield is increased ≈ 50-fold. Further, this solid upconversion material is utilized to demonstrate, for the first time, a broad-range oxygen sensing and 721 nm-driven heterogeneous and recyclable photoredox catalysis. These findings provide an important approach for regulating the behavior of triplet exciton in disorder solid materials to gain better upconversion performance, which will advance practical applications of organic photon upconversion in energy, chemistry, and photonics.

A spectrally-resolved dual-mode spinning-disk confocal microscopy is developed to monitor the 4D chemical heterogeneity of single V2O5 particles during cycling. A unique and irreversible transformation of V5+ to V3+ on a particle's bottom electric contact points has been unveiled for the first time. The coordination strategy between ethylene diamine tetraacetic acid and V3+ is proposed to inhibit V3+ precipitation effectively.

Microparticle cathode materials are widely used in secondary batteries. However, obtaining dynamic chemical heterogeneities of these microparticles is challenging, hindering in-depth mechanistic investigation of the underlying processes. For example, although vanadium pentoxide shows promise as an electrode material for zinc ion batteries, its poor performance's root cause is elusive. Herein, a fluorescence/scattering dual-mode spinning disk confocal microscopy-based approach is developed to visualize the 4D chemical heterogeneity of single V2O5 particles during cycling. Dual-mode in situ imaging identifies valence state changes of vanadium ions with high spatiotemporal resolution. A unique difference is observed between the scattering intensities of a particle's bottom electric contact points and the rest parts during the discharging process. In contrast, fluorescence intensity variation suggests high consistency across the particles. Correlative Raman, UV–Vis spectroscopy, and electrochemical impedance spectroscopy analyses suggest the precipitation of V3+ species at the bottom interface of the V2O5 electrode, leading to increased electron transfer resistance and compromised overall performance. A coordination strategy between ethylene diamine tetraacetic acid and V3+ is proposed for inhibiting V3+ precipitation, and its effectiveness is further verified by imaging and electrochemical impedance spectroscopy analyses. Insights from the imaging approach presented herein will enable the rational design of high-performance batteries.

This study addresses a critical challenge in the commercialization of perovskite solar modules by reducing photovoltage loss through the in situ formation of a surface conductive coordination polymer at the surface/interface of the perovskite film.

Despite the reported high efficiencies of small-area perovskite photovoltaic cells, the deficiency in large-area modules has impeded the commercialization of perovskite photovoltaics. Enhancing the surface/interface conductivity and carrier-transport in polycrystalline perovskite films presents significant potential for boosting the efficiency of perovskite solar modules (PSMs) by mitigating voltage losses. This is particularly critical for multi-series connected sub-cell modules, where device resistance significantly impacts performance compared to small-area cells. Here, an effective approach is reported for decreasing photovoltage loss through surface/interface modulation of perovskite film with a surface conductive coordination polymer. With post-treatment of meso-tetra pyridine porphyrin on perovskite film, PbI2 on perovskite film reacts with pyridine units in porphyrins to generate an iso-structural 2D coordination polymer with a layered surface conductivity as high as 1.14 × 102 S m−1, due to the effect of surface structure reconstruction. Modified perovskite film exhibits greatly increased surface/interface conductivity. The champion PSM obtains a record efficiency up to 23.39% (certified 22.63% with an aperture area of 11.42 cm2) featuring only 0.33-volt voltage loss. Such a modification also leads to substantially improved operational device stability.

The relationship between the bulk photovoltaic effect and cation symmetry is systematically investigated, leading to the first realization of a self-powered X-ray detector in metal-free perovskites. Reduced cation symmetry enhances both the dipole moment and crystal polarity, facilitating carrier migration while simultaneously passivating defects. Leveraging the nonlinear photocurrent response mechanism, the X-ray detector achieves ultra-high equivalent sensitivity at zero bias.

Metal-free perovskite (MFP) X-ray detectors have attracted attention due to biocompatibility and synthesizability. However, the necessity of high voltages for MFP X-ray detectors affects stability and safety. Although, the bulk photovoltaic effect (BPVE) with spontaneous electric field is a potential alternative for X-ray detection without high voltage, the constitutive relationship of BPVE in MFP remains unclear. Herein, the relationship between BPVE and cation symmetry is explored, and a self-powered X-ray detector is realized by BPVE in MFP for the first time. Theoretical studies show that cation symmetry reduction can distort the halide octahedron in one direction, which increases the dipole moment and crystal polarity to induce BPVE. The electric field from crystal polarity can drive the defect passivation by the equilibrium carrier and enhance the nonequilibrium carrier performance for BPVE. Then, polar MFP (mPAZE-NH4Br3 H2O) with excellent BPVE is designed. Due to the nonlinear response, the detector obtains a numerically recorded equivalent sensitivity (≈103 µC Gyair −1 cm−2) at 0 V. Moreover, the imaging performance is demonstrated and two image convolution kernels for it are constructed. Finally, it features continuous operation (20000 s) and temperature stability (-55–250 °C). It is believed that the method will further drive the application of MFP for X-ray detectors.

This review describes recent developments in the design and synthesis of metal–organic frameworks (MOF)/textile composites for the detoxification of chemical warfare agent and simulants with extensive discussion on the advantages and disadvantages of different methods. It also summarizes design rules for more active MOF catalysts and provides the implementation principles to achieve desired performances in practical conditions.

Threats from toxic chemical warfare agents (CWAs) persist due to war and terrorist attacks, endangering both human beings and the environment. Metal–organic frameworks (MOFs), which feature ordered pore structures and excellent tunability at both metal/metal cluster nodes and organic linkers, are regarded as the best candidates to directly remove CWAs and their simulants via both physical adsorption and chemically catalyzed hydrolysis or oxidization. MOFs have attracted significant attention in the last two decades that has resulted from the rapid development of MOF-based materials in both fundamental research and real-world applications. In this review, the authors focus on the recent advancements in designing and constructing functional MOF-based materials toward CWAs detoxification and discuss how to bridge the gap between fundamental science and real-world applications. With detailed summaries from different points of view, this review provides insights into design rules for developing next-generation MOF-based materials for protection from both organophosphorus and organosulfur CWAs to mitigate potential threats from CWAs used in wars and terrorism attacks.

This work reports on the engineering of distinctive 2D ultrathin ZnIn2S4 nanosheets with interlayer indium vacancies for highly efficient sonocatalytic lung cancer treatment.

Sonocatalytic therapy is gaining interest for its non-invasive nature, precise control, and excellent tissue penetration, making it a promising approach for treating malignant tumors. While defect engineering enhances electron and hole separation to boost reactive oxygen species (ROS) generation, challenges in constructing effective hole traps compared to electron traps severely limit ROS production. In this study, 2D ZnIn2S4-VIn nanosheets enriched are rationally designed with In vacancies for the efficient capture of electrons and holes, which has achieved substantial sonocatalytic performance in suppressing tumor growth. Compared to pristine ZnIn2S4 nanosheets, which possess a periodic electrostatic potential inherent in their structure, In vacancies effectively disrupt this potential field, promote the simultaneous separation and migration of charge carriers, and inhibit their recombination, thereby boosting ROS production and inducing tumor cell pyroptosis via the ROS-NLRP3-caspase-1-GSDMD pathway under ultrasound (US) irradiation. Furthermore, both pristine ZnIn2S4 and ZnIn2S4-VIn nanosheets exhibited remarkable biocompatibility. In vitro and in vivo antineoplastic experiments demonstrate that this sonocatalytic approach effectively promotes tumor elimination, underscoring the critical importance of defect-engineered optimization in sonocatalytic tumor therapy.