Efficient capture of Cs+ ions by two supertetrahedral cluster-based microporous metal chalcogenides in neutral and alkaline environments.

Though perovskites remain a vital component of the electronics industry and solar cell technology, the defects that occur in perovskite films due to uncontrollable crystallization and the fragility of ionic compounds remain serious limitations. The present study focused on synthesising a perovskite Cs0.1MA0.9PbI3 active layer with tailored configurations using transition metal sulphides (both pure and V-doped WS2 and MoS2) to enhance the device characteristics of perovskite solar cells (PSCs). By optimizing the organic-inorganic interface, the power conversion efficiency (PCE) of the optimised V-doped WS2-based PSC increased by 48% to reach an impressive 15.62%, representing a significant improvement from pure Cs0.1MA0.9PbI3. This enhanced output originates from the high photon absorption capability of V-doped WS2 and the efficient low-dimensional charge transport pathways, which together effectively increase the generation, separation, and collection of charge while minimizing recombination losses. In long-term stability testing, the optimized device retained 80% and 76% of its PCE after 1000 h under continuous illumination and at 70 °C, respectively. The proposed V-doped MS2- and WS2-based design offers reliable interfacial energy alignment and enriched charge transport, while also exhibiting great promise for scalable processing, positioning it as a useful candidate for next-generation energy conversion technologies.

Advances in transition metal sulfides: Synthesis, properties, and modification strategies for electrocatalysis and energy conversion applications

Fe-doping engineering of hierarchical NiS/Co2.67S4 nanoarrays as bifunctional electrocatalysts toward high-efficiency overall water splitting.

High-entropy transition metal sulfides (HESs) exhibit great potential as anodes for sodium-ion batteries owing to their synergistic entropy stabilization, lattice distortion and cocktail effects. However, potential phase separation caused by multi-component incompatibility severely limits their performance. Herein, we propose a low-mixing-enthalpy strategy through regulation of element chemical compatibility to precisely design high-performance HES anodes. This strategy enables the successful synthesis of a single-phase Co-Fe-Ni-Mn-Cr HES solid solution (HES-Cr). In contrast, inferior compatibility among components in Co-Fe-Ni-Mn-Mo HES (HES-Mo) leads to its phase separation. The electron delocalization in HES-Cr enhances conductivity and metal-sulfur bond covalency, while moderate lattice distortion alleviates volume changes and stress concentration during Na+ insertion/extraction and lowers the Na+ migration barrier. Consequently, the HES-Cr delivers excellent Na+ storage performance, including a high reversible capacity of 845.2 mAh g-1 at 0.2 A g-1 and ultra-high rate property of 497.5 mAh g-1 even at 40.0 A g-1 along with long stability, outperforming HES-Mo and most HES-based anodes. Furthermore, we propose a three-parameter descriptor to predict single-phase high-entropy materials across a broader compositional range. This work provides a new approach for rational design of single-phase HESs and deepens understanding of their composition-phase-performance relationships.

To accelerate the sluggish anodic oxygen evolution reaction (OER), the agglomeration restriction, the maximum utilization and enhancement of the electrical conductivity of active sites necessitate to design a highly exposed transition metal sulphides (TMSs)-based electrocatalysts with strong synergistic effect. Herein, we develop a space-confined hydrothermal synthesis method to fabricate Co0.5Fe0.5S2 nanocubes (CFS-nc) that exhibit restricted agglomeration and more exposed active sites for oxygen evolution. The electron transfer from the Fe to Co atoms through the synergistic effect in CFS-nc improves the metallic nature of the Co sites, thereby accelerating the OER activity. The cubic morphology, high surface area (37.68 m2 g-1) and porous structure (pore diameter of ∼13.97 nm) of CFS-nc expose the abundant catalytically active sites for rapid charge transfer. CFS-nc record an overpotential of 290 mV to achieve 10 mA cm-2 (η10), Tafel slope of 98 mV dec-1, low charge-transfer resistance (Rct = 1.1 Ω) and high double layer capacitance (Cdl = 6.1 mF cm-2) for the OER in alkaline media. In situ UV-vis spectroscopy analysis revealed that the OER mechanism follows the AEM pathway with rapid kinetics. Moreover, the CFS-nc∥Pt/C (+, -) electrolyzer exhibits a cell potential (η10) of 1.54 V, which is lower than that of the RuO2∥Pt/C (+, -) electrolyser (1.58 V) with excellent stability for 30 h for overall water splitting. This study introduces a promising approach to design efficient bimetallic TMS-based electrocatalysts for energy applications, particularly as anodic materials in water electrolysis.

Although they serve as the workhorse in the short-wavelength infrared window, performance of lead chalcogenide nanocrystals (NCs) in optoelectronic devices suffers from various atomic-level structural and electronic defects rooted in the facet-ligand interface. Considering the rock-salt structure, here we target the synthesis of PbSe NCs encased in eight (111) facets by introducing soluble chloride (or other halides) and alkanoate ions as mixed ligands in octadecene to release excessive strain within the conventional alkanoate ligand monolayer on the polar (111) facets. The resulting monodisperse octahedral PbSe NCs possess the defined (111) facets, as observed at a resolution of approximately one atomic layer by high-resolution transmission electron microscope (TEM), and a single facet-ligand coordination motif. The resulting NCs exhibit unique optical properties, formation of an orthorhombic three-dimensional superlattice, outstanding chemical stability against aerobic exposure, and excellent structural stability in solutions and thin films. As strong ligands, mixed alkanoate-chloride ligands yield small octahedral NCs─essential for high-efficiency photovoltaic devices─with high mass yields by controlling nucleation and growth. Results here reveal that ligand chemistry is the key toward atomically precise synthesis of colloidal NCs that are ideal for both fundamental research and technical applications.

Investigating the behavior, manipulation and transport of nanodroplets on the surface of solid films is critical for optimizing the functions of films and advancing diverse high-value applications across multiple fields. Using molecular dynamics simulations, we mainly investigate the moving behavior of water nanodroplets on the surface of MoS2/MoSe2 lateral heterostructure films. The results indicate that MoS2 exhibits more hydrophobic properties than the MoSe2 membrane, confirmed by the observation of a larger contact angle on the MoSe2 membrane. The van der Waals interactions were found to mainly dominate the wettability difference between MoS2 and MoSe2, where MoSe2 demonstrated a significantly stronger adsorption capacity for nanodroplets than MoS2. Based on this wettability difference, MoS2/MoSe2 lateral heterostructure films were designed to realize the directional migration, enrichment, and immobilization of water nanodroplets sequentially. Besides, effective regulation of the moving speed and direction of nanodroplets was achieved by constructing a MoS2/MoSe2 lateral heterostructure film with a wettability gradient. This research provides a theoretical basis and design insights for the development of microfluidic devices and droplet manipulation systems based on lateral heterostructures using two-dimensional transition metal chalcogenide materials.

Acid mine drainage (AMD) waters are a global environmental threat due to their extremely low pH (<3) and high metal loads. Acidophilic sulfate-reducing bacteria (aSRB) can mitigate AMD by reducing sulfate to sulfide, a proton-consuming process that also precipitates metals as metal sulfides. Although sulfate reduction has been observed in AMD waters, most characterized aSRB are only moderately acidophilic. Here, we examined the pH tolerance and proton stress adaptation of the complete organic acid-oxidizing aSRB Acididesulfobacillus acetoxydans. Continuous chemostat cultivations were operated across a pH gradient, reaching steady states from pH 5.0 (optimum) to pH 2.9. In subsequent batch incubations, biomass from a pH 2.9 chemostat remained metabolically active at pH 2.5. Transcriptomic profiles remained remarkably stable across conditions, except for the upregulation of the K+-transporting ATPase (kdpABC) at lower pH, suggesting an increased reliance on the chemiosmotic gradient to impede proton influx. Lipid analysis revealed increased core lipid saturation, midchain methylation, and a shift in priming precursors from leucine to valine at low pH, indicating reduced membrane permeability and more energy-efficient biosynthetic pathways. Together, these adaptations likely reduce proton entry, explaining how aSRB adapt to AMD-like acidity and unlock the pH bottleneck for AMD bioremediation and metal recovery.

We report the formation of 0Dߝ1D nanohybrds via two distinct strategies, utilising DNA as a template and a linker moiety in the controlled assembly of metal sulfide nanoparticles onto single-walled carbon nanotubes.

Sulfur vacancies (Svacs) are known to change the reactivity of transition metal sulfides, but their mechanistic role in small-molecule activation remains poorly understood. Here, we carried out synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS) and dispersion-corrected density functional theory (DFT-D3) calculations to elucidate how Svac sites on FeS2(100) surfaces promote nitric oxide (NO) dissociation. SR-XPS results reveal progressive Fe oxidation, Fe-N formation, and the growth of adsorbed oxygen species as a function of NO exposure. The N/O atomic ratio evolution suggests recombinative N2 desorption from the surface. DFT-D3 calculations show that the dissociative adsorption of NO is thermodynamically more stable on the defective FeS2(100) surface than on the defect-free surface. Based on the Brønsted-Evans-Polanyi relationship, dissociative adsorption of NO may be kinetically favorable on the defective FeS2(100) surface. Two possible pathways are proposed: (1) O-O bond formation at Svac sites and (2) oxygen-induced S-S bond cleavage to yield O-S species and new Smono. The present experimental-computational study demonstrates the atomic-level role of Svacs in NO activation on FeS2(100) and provides chemical insight into defect engineering of sulfide-based catalysts for selective nitrogen oxide conversion.

The slow kinetics of lithium carbonate (Li2CO3) nucleation/decomposition hinder voltage gap minimization in lithium-carbon dioxide (Li-CO2) batteries. Although symmetry-broken cation motifs can enhance reactivity, designing optimal catalysts remains challenging. Moving beyond cation-centric views, we recognize anions as active participants that regulate charge and stabilize intermediates, yet their degradation worsens the activity-stability trade-off. To address this, we develop a dual Φ descriptor quantifying anion-cation orbital coupling and reconstruction energy. It establishes a volcano correlation with the voltage gap in metal sulfides, showing that symmetry-broken units optimally balance binding and stability. Guided by this, we synthesize oriented WS2 rich in C4v configurations, achieving a record-low gap of 0.76volts and superior cycling (>1268 hours) among dichalcogenides. This work shifts the paradigm from cation-only tuning to synergistic anion-cation design, repositioning anions as co-catalytic architects. By linking orbital insights to performance, we provide a universal descriptor for developing efficient, stable Li-CO2 batteries.

Acidithiobacillus ferrooxidans, a chemolithoautotrophic iron- and sulfur-oxidizing acidophile, is a key contributor to industrial-scale copper metal bioleaching. These cells naturally produce magnetosomes, and they may serve as an emerging platform for magnetosome bioproduction, as magnetotactic bacteria (MTB) are difficult to cultivate and genetically modify. Here, we manipulated the expression of the endogenous homologues to the magA and mamB genes in A. ferrooxidans, which are implicated in iron transport required for magnetosome synthesis. Modulation of mamB had no impact on cell behavior. Overexpression of magA increased magnetosome formation and magnetic responsiveness, and these effects were attenuated by CRISPRi knockdown of magA. The augmented magnetosome formation in the magA overexpression cells also led to enhanced bioleaching of pyrite, which is weakly paramagnetic, and this could be further enhanced by the addition of an external magnetic field. These results confirm that magA plays a critical role in magnetosome formation in A. ferrooxidans and that the magnetosome expression can be enhanced through genetic engineering. In addition, these results demonstrate the potential to improve metal sulfide bioleaching through manipulation of genes involved in magnetosome formation.

The selective detection of ammonia, a hazardous atmospheric pollutant, at room temperature remains a key challenge for high-performance gas sensor development. In this study, three ZnIn2S4 (ZIS)-based metal sulfide heterojunctions including Ag2S/ZIS, CuS/ZIS, and NiS/ZIS were synthesized via a cation exchange strategy, where the formation of well-defined heterostructures led to significantly enhanced sensing performance. Among them, the Ag2S/ZIS sensor exhibited ultra-high sensitivity, achieving a response of 2.35 to 10ppm ammonia at room temperature. Furthermore, a neural network model was employed to analyze the response curves of the three heterojunctions under varying gas concentrations. The results revealed that all three sensors achieved recognition accuracies exceeding 87.5%, with the Ag2S/ZIS heterojunction showing the highest accuracy, highlighting its superior performance compared to the other two sensors.

Nanocrystals (NCs) serve as versatile building blocks for the creation of functional materials with NC self-assembly offering opportunities to enable novel material properties. Here, we demonstrate that PbS NCs functionalized with strongly negatively charged metal chalcogenide complex (MCC) ligands, such as Sn2S64- and AsS43-, can self-assemble into all-inorganic superlattices with both long-range superlattice translational and atomic-lattice orientational order. Structural characterizations reveal that the NCs adopt an unexpected edge-to-edge alignment, and numerical simulation clarifies that orientational order is thermodynamically stabilized by many-body ion correlations originating from the dense electrolyte. Furthermore, we show that the superlattices of Sn2S64--functionalized PbS NCs can be fully disassembled back into the colloidal state, which is highly unusual for orientationally attached superlattices with atomic-lattice alignment. The reversible oriented attachment of NCs, enabling their dynamic assembly and disassembly into effectively single-crystalline superstructures, offers a pathway toward designing reconfigurable materials with adaptive and controllable electronic and optoelectronic properties.

Developing a feasible approach to improve both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance of MoS2 is important for the utilization of low-cost and earth-abundant non-noble metals toward efficient water splitting. Herein, we report a hydrothermal strategy to construct binary metal sulfide heterostructures supported on reduced graphene oxide (RGO) by utilizing polyoxometalates as precursors. By integrating the transition-metal sulfides (MxSy = FeS, NiS, CoS2) with MoS2 nanosheets, all of the heterostructures achieved obviously enhanced bifunctional activity due to the interfacial interaction and synergism between MxSy and MoS2. Consequently, the NiS-MoS2/RGO and FeS-MoS2/RGO catalysts exhibited the lowest overpotentials at the current density of 10 mA cm-2, which required only 132 mV for the HER and 231 mV for the OER, respectively. More importantly, a low cell voltage of 1.58 V was achieved for delivering an overall water-splitting current density of 10 mA cm-2 by assembling the NiS-MoS2/RGO and FeS-MoS2/RGO into an electrolyzer. This work provides a feasible strategy for designing bimetal heterostructures to improve the water splitting performance of MoS2-based catalysts.

Sulfur-containing wastes are typical pollutants generated from oil and gas extraction, petroleum refining, and fossil fuel combustion, with annual global emissions reaching tens of millions of tons. Traditional treatment technologies rely on end-of-pipe control, suffering from high energy consumption, substantial carbon emissions, severe secondary pollution, and low resource utilization efficiency. Electrocatalytic conversion driven by renewable electricity enables the directional valorization of sulfur-containing pollutants under mild conditions, providing an alternative route for the green upgrading of sulfur resources. This review systematically summarizes the research progress in electrocatalytic valorization technologies for waste sulfur-containing species. Starting from the fundamental reaction principles, we elaborate the electrocatalytic conversion routes, reaction mechanisms, catalyst design, and system optimization strategies for four typical sulfur-containing substrates, including inorganic sulfides, sulfur oxides, organosulfur wastes, and metal sulfide minerals. It highlights the core technological innovations of direct interfacial electrocatalysis, redox mediator-mediated indirect electrocatalysis, and paired electrolysis. Moreover, the key challenges in anti-sulfur-passivation electrodes, reactor scale-up, reaction process design, and adaptation to complex industrial systems are outlined, and future perspectives are proposed. This review aims to provide theoretical and technical guidance for the green and low-carbon valorization of industrial sulfur-containing pollutants.

Two-dimensional materials are promising candidates for thermoelectric devices due to their superior structural flexibility and tunable electronic and thermal properties. The recent discovery of group III-V-VI semiconducting monolayers offers new promise in this regard. In this work, we investigate the ballistic thermoelectric transport performance of monolayer InAsSe using density functional theory combined with the non-equilibrium Green's function method. We find that both electronic and phononic transport along a-axis (zigzag) and b-axis (distorted armchair) are strongly asymmetric due to the markedly anisotropic electronic and phonon band dispersion. Interestingly, the electronic and phononic transport exhibit similar directional dependence, which offers the opportunity to obtain a comparable thermoelectric figure of merit along two crystalline orientations. Moreover, in contrast to monolayer transition metal chalcogenides, we find that the thermoelectric performance is also similar between p- and n-doped monolayer InAsSe, such comparable transport characteristics for both carrier types being advantageous for practical thermoelectric module integration. At 300 K, the optimal figure of merit along the a-axis (b-axis) is 0.71 (1.02) for p-type and 0.65 (0.67) for n-type. Upon increasing the temperature to 600 K, all these optimal values exceed 1.5. These findings suggest that monolayer InAsSe is a promising thermoelectric material with transport characteristics distinct from those of previously reported monolayers.

The energy-free activation of ambient molecular oxygen (O2) to singlet oxygen (1O2) under neutral conditions is highly desirable for green oxidation chemistry, yet remains fundamentally limited by sluggish proton-coupled *OOH formation and desorption. Here, we engineer an interfacial proton-relay microenvironment between MoS2 and CuCl that enables self-driven O2-to-1O2 conversion without external energy inputs. Electron-deficient sulfur sites act as a proton reservoir by forming S-Hads species, facilitating directional proton migration through Cu-S-Mo channels to activate adsorbed O2 on electron-rich Cu sites. This coupled electron-proton relay accelerates *OOH hydrogenation while maintaining moderate *O2/*OOH binding, effectively suppressing O─O bond cleavage and favoring a 1O2-dominated pathway. As a result, the system achieves quantitative pollutant removal and sustained operation for over 16 h in pilot-scale membrane filtration. This interfacial design is broadly applicable to transition metal sulfides, offering a general strategy to overcome proton-transfer limitations and advance autonomous catalytic platforms for sustainable oxidation and environmental remediation.

Quantum tunneling offers a fascinating paradigm for orchestrating spatial charge transport in artificial photosynthesis. However, precisely manipulating electron tunneling across well-defined heterointerfaces remains a formidable challenge, with conventional designs largely confined to classical Semiconductor–Insulator–Metal (S–I–M) architectures. Herein, we report a conceptual endeavor by fundamentally departing from the traditional S–I–M model, constructing a unique and novel semiconductor–insulator–ligand/metal tunneling platform. Specifically, an ultrathin insulating poly(sodium 4-styrenesulfonate) (PSS) layer is engineered onto a transition metal chalcogenide (TMC, e.g., CdS) substrate. Subsequently, poly(diallyldimethylammonium chloride) (PDDA)-capped metal nanocrystals (M@PDDA, M = Au, Pd) are precisely anchored via electrostatic self-assembly, yielding well-defined TMC@PSS/M@PDDA heterostructures. Distinct from conventional systems, the PDDA ligands synergistically couple with the metal core to form an integrated, highly potent electron capture center driven by the Schottky-junction effect. This unique synergistic driving force triggers non-classical, directional electron tunneling from the photoexcited TMC substrate directly through the insulating PSS barrier. Benefiting from this advantageous quantum tunneling, TMC@PSS/M@PDDA heterostructures demonstrate significantly enhanced and multifarious visible-light-driven photoredox activities including selective organic transformations and H2O2 production. This work establishes an elegant conceptual paradigm for decoding and customizing quantum tunneling pathways, offering profound fundamental insights into advanced solar energy conversion.