Scalable ambient-air (relative humidity > 40%) fabrication of wide-band-gap (WBG, >1.75 eV) perovskite cells is critical for commercialization of all-perovskite tandem solar cells yet faces challenges from inhomogeneous crystallization and moisture-induced degradation. Herein, we introduce a strategy leveraging molecularly designed poly(potassium 4-styrenesulfonate) (PKSS). This design exploits strong sulfonate-perovskite interactions, further reinforced by electron-delocalizing aromatic ring. The synergistic effect suppresses pinhole defects and promotes uniform crystallization in vacuum-quenched large-area films. Upon annealing, PKSS self-assembles into a hydrophobic capping layer that simultaneously blocks moisture ingress and passivates surface defects. This synergistic approach yields efficient WBG perovskite solar cells (0.077 cm2) with a record open-circuit voltage (VOC) of 1.38 V and enables monolithic all-perovskite tandem cells with a certified efficiency of 29.34%. Crucially, demonstrating scalability in ambient air, we achieve efficiencies of 18.48% (certified 18.11%, avg. VOC 1.381 V) for WBG perovskite modules and 25.35% for all-perovskite tandem modules over areas of 20.45 cm2.

The manipulation of the electronic configuration of transition metals has garnered significant attention for water treatment. However, the underlying mechanism of how regulating the occupancy of antibonding orbitals enhances pollutant degradation remains unclear. Herein, we select Prussian blue derivative (Co3O4/NiO) as the model system to precisely tune the pi* antibonding orbital occupancy, which demonstrate remarkable efficiency in degrading sulfachloropyridazine (SCP) in pharmaceutical wastewater, achieving a high rate constant (k1 = 0.76 min-1). In Co/Ni bimetallic oxides, electron donation from Ni2+ to Co sites renders them electron-rich. Relative to conventional Co3O4, this elevates the Fermi level and alters the antibonding orbital population (t2g 6 eg 0 -> t2g5 eg1), thereby enhancing peroxymonosulfate (PMS) activation. X-ray absorption spectroscopy (XAS) and DFT calculations show that t2g electron excitation enhances eg filling, increases pi* orbital occupancy, and thereby promotes the electron transfer between Co 3d of the catalyst and O 2p of PMS, leading to efficient ROSs generation.

Supramolecular isomerism offers a unique platform for investigating the relationship between molecular structures and physicochemical properties. However, such isomerism still remains rare, particularly packing-induced isomers, owing to challenges in controlling diverse coordination modes and intermolecular interactions. Herein, by controlling the intermolecular π-stacking between the monodentate, highly conjugated PhSQ ligands, we synthesized a pair of viologen-based copper(II) isomers, CuCl2(PhSQ)2 (denoted as 1 and 2) (PhSQ = N-(4-sulfophenyl)-4,4'-bipyridinium). Single-crystal X-ray diffraction analysis reveals that isomer 1 assembles into a supramolecular organic framework through π-stacking interactions, whereas 2 adopts a densely packed structure composed of A−B-style supramolecular chains via π-stacking. Notably, isomer 1 exhibits distinct chromic behavior upon exposure to light and thermal stimuli, whereas 2 shows no such color change. Furthermore, Isomer 1 displays superior structural stability and greater sensitivity to light and heating stimuli relative to 2. The outstanding performances of isomer 1 are presumably attributable to its more abundant π-stacking interactions within its framework. Meanwhile, it also shows significantly higher absorbance and a higher photothermal conversion efficiency of 31.58%, compared with 2 of 25.03%. These results not only provide valuable insights into further probing the physicochemical properties and structural assembly of supramolecular materials based on intermolecular π-π stacking interactions but also lay a foundation for their rational design and application expansion.

Overcoming the symmetric electronic structure of single-atom catalysts (SACs) to promote the cleavage of O-O bond remains critical for efficient H2O2 activation. Herein, the high-loading Fe SACs (FeN1C2/C2N, 7.2 wt%) is designed via in-situ carbon defect engineering, which breaks the symmetric electronic structure through the nonplanar asymmetric coordination of Fe. DFT calculations and characterizations reveal that compared to the planar symmetric Fe-N-2 structure, N-1-Fe-C-2 coordination modifies d-p orbital hybridization, inducing the spin state of Fe from low-spin (LS, t(2) g: up arrow down arrow, up arrow down arrow, up arrow down arrow; eg: _, _, _) to high-spin (HS, t(2) g: up arrow down arrow, up arrow, up arrow; eg: up arrow, up arrow; _). The HS state weakens the coupling between *H2O2 and Fe 3d orbitals, promoting H2O2 decomposition into abundant center dot OH, further achieving electron-rich pollutant Sulfamerazine (SMR) degradation with the rate constant of kobs= 0.3308 min(-1). Additionally, such nonplanar asymmetric coordination releases the N atoms adjacent to the Fe sites, allowing them to form electron-transfer channel with SMR, which establishes nonradical electron transfer pathway (ETP). Pollutant pre-adsorption enables center dot OH to attack the target in situ along an ultrashort pathway, resulting in an efficient ETP-assisted radical oxidation mechanism. Overall, this work provides new insights into SACs design and a novel perspective for Fenton-like systems application.

Precise modulation of electron distribution in photocatalysts remains a pivotal challenge in solar-driven photocatalytic water decontamination. In this work, orbital population engineering is developed in oxygen-deficient tungsten oxide (OPE-WO3-x) to redistribute electrons from W 5dxz/dyz to the W 5dxy orbital. This redistribution prolongs charge carrier lifetime and enhances W 5d (primarily conduction band) electron donation. Theoretical calculation unveils a direct excited-electron transfer from populated W 5dxy to the higher-lying W 5dx 2 -y orbital within an optimized spin-polarized electronic structure. Femtosecond transient absorption spectroscopy (fs-TAS) confirms accelerated excitation (due to W 5dxy donation), suppressed charge recombination, extended carrier lifetime, and broadened light absorption. The optimized excited-state dynamics, together with spin-polarized state, strongly support facilitated intersystem crossing into long-lived triplet states. Consequently, OPE-WO3-x achieves complete degradation of gatifloxacin (10 mu M) within 30 min under simulated solar light, with a rate constant (0.21 min- 1) 10.5-fold higher than conventional WO3-x (0.020 min- 1). Unlike indirect reactive oxygen species dominated pathways, degradation mainly proceeds via direct electron transfer process (ETP) mediated by W-N bond through the W 5dz2 orbital channel. This work pioneers orbital population engineering for designing efficient photocatalysts, providing a strategy for water decontamination through the ETP mechanism in photocatalysis.

Chiral perovskite nanocrystals (PNCs) represent a compelling material platform for spin light-emitting diodes (spin-LEDs) owing to their solution processability, high photoluminescence quantum yields (PLQY), narrow and tunable band emission properties, together with the chiral-induced spin selectivity (CISS) effect that enables efficient spin polarization injection without requiring ferromagnetic injectors or external magnetic fields. This review summarizes the synthesis approaches for constructing chiral PNCs, including chiral ligand engineering, template-assisted growth, two-dimensional (2D) chiral metasurfaces coupling, and core-shell structure design. Besides, diverse optoelectronic modulation strategies of chiral PNCs, such as halide composition adjustment, external stimuli modulation, and integration with photonic architectures, are discussed, which are crucial for the fabrication of high-performing spin-LEDs with wavelength-tunable emission, high external quantum efficiency (EQE), and dynamically controllable circularly polarized electroluminescence (CP-EL). Finally, the key challenges and prospects for chiral PNC-based spin-LEDs are outlined, highlighting the viability of cost-effective, highly efficient, and stable spin-LED devices for future optoelectronic technologies.

The inherent atomic disorder in amorphous materials leads to unsaturated atomic sites or dangling bonds, effectively modulating the material's electronic states and rendering it an ideal platform for the growth of single atoms. Herein, the electronic structure of isolated cobalt atoms anchored on amorphous carbon nitride (Co-ACN) is modulated through a substrate amorphization engineering, enabling the thorough removal of pazufloxacin (PZF) in 1 min with a high reaction rate constant (k1) of 3.504 min-1 by peroxymonosulfate (PMS) activation. Experiments and theoretical calculations reveal that Co-ACN exhibited a higher coordination environment (Co-N3) compared to crystalline Co-CCN (Co-N2). Meanwhile, the t2g energy level enhancement of Co 3d orbital promotes electron transition from t2g to eg, inducing more unpaired electrons and thereby driving the transition from a low-spin state (LS, t2g 6eg 1) to a high-spin state (HS, t2g 5eg 2). The HS Co-ACN optimized the d-band center, boosted the electronic transfer, and weakened the interaction between Co 3d and O 2p orbitals of HSO5 -, thereby enabling nearly 100% selective singlet oxygen (1O2) generation, whereas Co-CCN yielded coexisting reactive oxygen species (ROS). This work opens up a new paradigm for regulating the electronic structure of single-atom catalysts at the atomic scale.

Solar-light-driven photocatalysis is a green and efficient technology to immobilize high-toxic and radioactive uranium (U). However, a great challenge is to develop photocatalysts with simultaneous elevated conduction band (CB) potential and rapid charge carrier separation rate. Herein, spin-state engineering in d 0 WO 3 through (110) facet-confined oxygen vacancies (OVs) is proposed. Anchoring OVs at the symmetry-broken (110) facets induces low-spin W III (d 3 ) generation, delocalizing CB electrons and elevating CB by −0.86 V versus NHE due to higher electron occupancy in π antibonding orbitals. Density functional theory (DFT) calculations combined with femtosecond transient absorption spectroscopy (fs-TAS) reveal that triplet (T)-dominated spin-polarized electron delocalization significantly disrupts the charge carrier recombination pathway. Experiments and theoretical calculations confirm the enhanced interfacial charge transfer via O bridging between W 5d and U 5f provides a W 5d → U 5f directional electron transfer channel. Thus, the developed (110)-WO 2.35 achieves high photocatalytic activity for U(VI) removal from water under simulated solar light, with a reduction efficiency of 98.0% ( C 0 = 10 mg L −1 ) and a reaction rate constant ( k 1 ) of 0.022 min −1 , which is 4.1 times higher than the conventional WO 3 . This work pioneers atomic-scale spin-orbital synergy in d 0 photocatalysis, offering a novel strategy for radionuclide remediation.

Developing an effective and powerful photocatalyst is important to its practical application in water treatment area, like emerging contaminants removal in water. Herein, through a synergistic strategy of N-doping and carbon quantum dots (CQDs)-loading on WO3 nanoflowers, CQDs/N-WO3 was designed, which exhibited excellent photocatalytic performance due to modulated electronic structure. Both experimental characterization and theoretical calculation confirmed that the synergistic effect accelerated the electron transfer ability from O2p to W5d, thus promoting the photogenerated electron and hole separation efficiency owing to the increased W5d orbital electron density. The optimum photocatalyst achieved 100 % removal of gatifloxacin (GAT) with a high reaction rate constant (k1) of 0.055 min- 1 in 60 min under simulated solar light. Moreover, quenching experiment and radical detection demonstrated that the main reactive oxygen species (ROS) changed from center dot OH (WO3 and N-WO3) to O2 center dot- (CQDs/N-WO3) for GAT removal. Density functional theory (DFT) calculation based on Fukui index further indicated the reactive sites of GAT were available for electrophilic attack. The internal mechanism was also deduced that after N doped and CQDs loaded on WO3, narrowed band gap and increased utilization of visible light were observed. Moreover, the high electron density of N sites was more conducive to hole capture, and CQDs enhanced the electron transport as electron acceptor and transporter. The synergistic strategy of doping and loading opens a new perspective for modulating the electronic structure of catalysts, and provides a reference for regulating the ROS types in Fenton-like reactions for the removal of emerging contaminants in water.

Simultaneous degradation and detoxification during pharmaceutical and personal care product removal are important for water treatment. In this study, sodium niobate nanocubes decorated with graphitic carbon nitride (NbNC/g-C3 N4 ) were fabricated to achieve the efficient photocatalytic degradation and detoxification of ciprofloxacin (CIP) under simulated solar light. NaNbO3 nanocubes were in-situ transformed from Na2 Nb2 O6 H2 O via thermal dehydration at the interface of g-C3 N4 . The optimized NbNC/g-C3 N4 -1 was a type-I heterojunction, which showed a high conduction band (CB) level of -1.68 eV, leading to the efficient transfer of photogenerated electrons to O2 to produce primary reactive species, center dot O2 -. Density functional theory (DFT) calculations of the density of states indicated that C 2p and Nb 3d contributed to the CB, and 0.37 e- transferred from NaNbO3 to g-C3 N4 in NbNC/g-C3 N4 based on the Mulliken population analysis of the built-in electric field intensity. NbNC/g-C3 N4 -1 had 3.3- and 2.3-fold of CIP degradation rate constants ( k1 = 0.173 min-1 ) compared with those of pristine g-C3 N4 and NaNbO3 , respectively. In addition, N24, N19, and C5 in CIP with a high Fukui index were reactive sites for electrophilic attack by center dot O2 -, resulting in the defluorination and ring-opening of the piperazine moiety of the dominant degradation pathways. Intermediate/product identification, integrated with computational toxicity evaluation, further indicated a substantial detoxification effect during CIP degradation in the photocatalysis system. (c) 2025 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Lead halide perovskites hold great promise for photovoltaics and optoelectronics, yet ion migration continues to challenge their long-term stability. Here, combining first-principles calculations and machine learning molecular dynamics, we unravel the interplay between perovskite octahedral lattice dynamics and energy barrier associated with ion migration. Our results show that B-site substitution, particularly with alkaline-earth and lanthanide elements, notably strengthens lattice interactions, restrains octahedral oscillation, and increases iodine-migration barriers, outperforming the commonly used A-site and X-site substitutions and interstitial doping. Moreover, the enhanced barrier aligns with the geometric factor of μτ (tolerance-octahedral product), underlining the superior effectiveness of co- and multiple-element B-site doping in lattice stabilization and ion migration suppression. Experimental validation with exemplary hysteresis-free Eu-Ca–doped perovskite single crystals demonstrates remarkable improvements in ambient stability and transport properties. These findings highlight B-site engineering as an effective microstructural strategy for controlling ion migration, with important implications for stable and lead-reduced perovskite devices.

Photocatalysis is a green and efficient technology for degradation of pharmaceuticals and personal care products (PPCPs) in water, and development of novel photocatalyst with high activity is urgently needed. In this study, a class of composite photocatalysts (KT-x(CQDs)-y(T)), i.e., carbon quantum dots (CQDs) decorated K2Ti6O13 nanotube (KTNT), were prepared via a facile hydrothermal treatment combined with calcination. The optimized photocatalyst (KT-2.0-300) exhibited high photocatalytic activity for naproxen (NPX) degradation, achieving 100 % degradation efficiency within 20 min. In addition, the pseudo-first-order rate constant (k(1)) for KT-2.0-300 was similar to 52 times higher than that for neat KTNT without CQDs decoration. Density functional theory (DFT) calculations further demonstrate that due to the introduction of CQDs, the electrons of Ti 3d are in a spin polarized state in KTNT, which greatly inhibits the recombination of photogenerated electron-hole pairs. In addition, CQDs can receive electrons from O 2p and transfer them to Ti 3d, which further improves the electron transfer efficiency and promotes reactive species generation. Photogenerated holes (h(+)) and hydroxyl radical (center dot OH) were demonstrated the primary reactive species during NPX degradation. Then based on identification of degradation intermediates and DFT calculation on Fukui index of NPX, the speculative pathway of NPX degradation involved three primary routes: demethoxylation, decarboxylation and dehydroxylation. Deep degradation of NPX in the photocatalysis system also leads to efficient detoxification of NPX. This study presents a feasible method for synthesis of titanate-based photocatalysts with significant potential for the removal of PPCPs from wastewater.

Heterogeneous catalysis, particularly transition metal (TM) catalysis, has been widely applied in wastewater purification fields such as Fenton-like technology due to the high efficiency and low cost. Generally, the spin state of TM would essentially impact the d orbital electronic structure, further influencing the catalytic performance of TM, so the spin state regulation to enhance catalytic activity has become a hot-spot research area now. However, there is little research to summarize the progress of TM spin state regulation for Fenton-like catalysis. Firstly, this review discusses the fundamental relationship between electron spin and Fenton-like catalysis, including the spin state characterization, the impact of spin-orbit coupling, regulation of the spin state of the active center for TM in catalysts, as well as the interaction between Fenton-like catalysis and spin state of TM. Secondly, the review summarizes the leading catalysts and their advantages in terms of reaction pathways and efficiency in Fenton-like reactions for water remediation. This review offers useful information for the design of spin catalysts for water treatment by Fenton-like catalysis.

Perovskite/silicon tandem solar cells (TSCs) attract intensive attention because of their potential to deliver power conversion efficiencies (PCE) beyond those of their single-junction counterparts. However, the performance and stability of tandem devices are limited by defect-assisted non-radiative recombination and light-induced halide segregation in wide-bandgap (WBG) perovskite sub-cells. Here, 2-aminoethanesulfonamide hydrochloride (AESCl), with multi-point chelation sites and bridging capability, is incorporated into a 1.68 eV WBG perovskite to comprehensively passivate defects at grain boundaries and surfaces. As a result, AESCl-treated perovskite films show suppressed halide segregation and a champion WBG single-junction solar cell achieves an impressive efficiency of 22.80% with an open-circuit voltage of 1.286 V due to reduced non-radiative recombination. The efficient WBG perovskite sub-cells enable perovskite/silicon TSCs to reach a champion PCE of 30.36% over 1 cm2. Moreover, the tandem devices retain over 96% of their initial efficiency after operation for 1068 h under continuous AM 1.5G illumination at 25 degrees C in ambient air.

The low affinity caused by the mismatched surface energies between the perovskite precursor solution and the underlayer is the main reason for the poor coverage of perovskite films, which is also accountable for the pinholes in the perovskite films. To solve this problem, amphiphilic soybean lecithin (denoted as SL), which has two long aliphatic chains, is incorporated into the PbI2 precursor solution. The amphiphilic nature of SL improves the coverage of perovskite films on hydrophobic PTAA, which is conducive to the fabrication of large-scale devices. In addition, the C═O, P═O, and quaternary ammonium groups in the zwitterion segment can passivate charged defects, thus decreasing the defect density of perovskite films. Notably, the power conversion efficiency (PCE) of the corresponding perovskite solar cells (Pero-SCs) with an active area of 0.1 cm2 increased from 20.12 to 22.93%. Furthermore, the SL-doped devices with a larger active area of 1.1 cm2 achieved the champion PCE of 18.32%. Moreover, the SL-doped Pero-SCs showed better humidity stability than did the control Pero-SCs.

Colloidal quantum dots (QDs) have demonstrated great potential as building blocks in various photoelectrochemical (PEC) devices that enable highly efficient optical-electrical-chemical conversion. However, the photogenerated electrons and holes in most of the QDs are generally confined to cause inefficient charge carrier separation and extraction for limited PEC performance. Herein, a two-step surface engineering technique is developed to manipulate the photoinduced charge carrier kinetics in a classical InP/ZnSeS QD system through the construction of Zn vacancies (VZn)-related under-coordinated (UC) Se/S sites and subsequent Cl- ligand exchange. It is revealed that the introduced VZn-UC Se/S sites can act as hole-trapping centers to facilitate the charge separation, and the Cl- ligands further induced a local internal electric field in QDs to drive a more efficient carrier extraction. As a result, the optimized QDs-based PEC device delivers a maximum photocurrent density of 12.1 mA cm-2 in PEC hydrogen evolution (1 sun, AM 1.5G) and an exceptional responsivity of 1.22 A W-1 in self-powered PEC photodetection. This study deepens the understanding of the intricate interplay between surface modulation and optoelectronic properties in QDs, offering a universal strategy to design cost-effective and high-performing QDs-based PEC devices for solar energy conversion and light detection applications.

Self‐assembled monolayers (SAMs) have substantially advanced the efficiency of inverted perovskite solar cells (PSCs), yet weak interfacial adhesion to transparent conductive oxide (TCO) substrates and perovskite compromises both scalability and thermal stability. Here, an electrostatically enhanced anchoring strategy (EEAS) is presented using sulfadiazine (SDZ) molecules to deprotonate phosphonic acid groups in SAMs, generating phosphate anions that strengthen electrostatic interactions with the positively charged TCO substrates. The protonated SDZ species concurrently establish strong coordination interactions with the buried perovskite interface. This approach enables the formation of uniform and robust buried interfaces while improving perovskite crystallinity and facilitating charge extraction. The resulting PSCs achieve a certified efficiency of 26.23% (steady‐state 25.42%) over 1 cm 2 areas. This EEAS is scalable, enabling 20.7‐cm 2 modules with a PCE of 24.72%. The devices demonstrate exceptional operational stability, retaining over 94% of their initial efficiency after 1000 h of continuous illumination at 65 °C (ISOS‐L‐2).

Removal of emerging contaminants has drawn great concern due to their potential high risk to eco-environment system and human health. In this study, an emerging and broad-spectrum anticancer pharmaceutical, larotrectinib (LOXO), was focused on to achieve its degradation in water. A heterogenous peroxymonosulfate (PMS) activation system was constructed by using a comet-like Co-based metal-organic framework (Co-MOF) with TiO2 nanoparticles decorated. The optimized material (TiO2/Co-MOF1) showed high PMS activation efficiency, and thus 90.1 % of LOXO could be quickly degraded within 10 min. Scavenger quenching tests and electron paramagnetic resonance (EPR) analysis indicated that both radicals (center dot OH and SO4 center dot-) and non-radical species (1O2) contributed to LOXO degradation. The two main components of Co-MOF and TiO2 nanoparticles in the composite showed a synergetic effect on PMS activation: Co-MOF offered coordination cobalt for PMS activation, while TiO2 provided abundant -OH groups for interface complexation to promote the electron transfer. In addition, 1O2 originates from directional conversion of center dot O2- after PMS activation at the material's surface. Moreover, density functional theory (DFT) calculation suggests that the atoms in LOXO with high Fukui index (f -) representing electrophilic attack are the reactive sites. Toxicity analysis based on quantitative structure-activity relationship (QSAR) verifies the reduced toxicity of degraded intermediates/products. This work proposed an available technology to efficiently activate PMS for anticancer drugs degradation through both radical and non-radical pathways in wastewater.

Asymmetric single-atom catalysts (ASACs) have attracted much attention owing to their excellent catalytic properties. However, the relationship between asymmetric coordination and the spin states of metal sites remains unclear. Additionally, the modulation of reactive oxygen species in Fenton-like reactions remains challenging. Herein, a novel strategy is reported for the rational design of highly loaded Co ASACs (CoN1C2/C2N) immobilized on three-dimensional flower-like C2N using an in situ-generated carbon defect method. In particular, the asymmetrically tricoordinated CoN1C2/C2N exhibited excellent catalytic activity for sulfachloropyridazine degradation, with a turnover frequency of 36.8 min-1. Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration (t2g6eg1) to the high-spin configuration (t2g5eg2) owing to asymmetric coordination. The high-spin Co 3d orbital in CoN1C2/C2N possessed more unpaired electrons and therefore, had a strong ability to gain electrons from the O 2p orbitals of HSO5-, boosting d-p orbital hybridization. More importantly, the spin-electron filling in the sigma* orbital of high-spin Co 3d-O 2p accelerated the desorption of *SO5 center dot-, which acted as a rate-limiting step in the reaction, thus facilitating more 1O2 generation. This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state, paving the way for advancements in environmental remediation and energy conversion applications. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.