Abstract Density functional theory (DFT) investigations were performed on a diverse library of iron(II) dichloride complexes bearing iminopyridine (ImPy) ligands to establish robust structure–property relationships governing their electronic and vibrational behavior. The pronounced structural flexibility of ImPy ligands generates multiple coordination motifs and spin-state manifolds, which frequently complicate experimental characterization and spectroscopic assignment. By systematically correlating geometric descriptors with infrared (IR) and ultraviolet-visible (UV–Vis) signatures, we identify reliable markers of both spin states and local coordination environments across mononuclear and dinuclear complexes. The computational trends show strong agreement with experimental benchmarks, establishing a diagnostic spectroscopic interpretation framework of coordination geometry and spin states in structurally flexible ImPy–Fe complexes, even in the absence of crystallographic data. Ultimately, this study offers a valuable framework for the informed design of next-generation iron (pre)catalysts, helping to tune electronic landscapes and spin-state populations for optimized reactivity.
Abstract Efficient purification of polymer-grade ethylene (C2H4) from methanol-to-olefins (MTO) products remains challenging because of the similar physicochemical properties of light hydrocarbons. Herein, we report a fluorinated metal–organic framework, CF3-Ni, featuring uniformly distributed trifluoromethyl (−CF3) groups that construct a fluorine-rich polar pore environment for selective hydrocarbon recognition. CF3-Ni exhibits preferential adsorption toward C3 hydrocarbons, with an affinity sequence of C3H6 > C3H8 > C2H4. At 298 K and 1 bar, it shows a C3H6/C2H4 IAST selectivity of 9.3 and a moderate C3H6 adsorption enthalpy of 38.4 kJ mol–1, enabling strong yet reversible host–guest interactions. Breakthrough experiments demonstrate efficient separation of C3H6/C2H4 mixtures over a wide range of feed compositions, affording polymer-grade C2H4 (>99.95%) with a maximum productivity of 7.4 mol kg–1 and simultaneous recovery of high-purity C3H6. Notably, one-step purification of polymer-grade C2H4 is achieved from a ternary C3H6/C3H8/C2H4 mixture, even under humid and elevated-pressure conditions. DFT calculations and in situ FT-IR spectroscopy reveal that C–H···F interactions contribute to the preferential binding of C3H6. This work demonstrates fluorinated pore chemistry as an effective strategy for practical olefin purification.
Abstract We report the synthesis and structural characterization of a series of bi- and tetranuclear Cu(I) complexes based on symmetrical triazene ligands. These ligands, which feature a central −N═N–N– backbone for metal coordination, offer tunable electronic and steric environments through substitution at the aryl ring with electron-donating and electron-withdrawing groups. A library of triazene ligands was prepared via diazotization and coupling strategies, followed by metalation under mild conditions to afford discrete Cu(I) assemblies. X-ray crystallographic analysis of six representative examples revealed both dinuclear and tetranuclear Cu(I) cores exhibiting short Cu···Cu distances (<2.6 Å), consistent with intramolecular cuprophilic interactions. DFT and experimental studies indicate the preference for dinuclear or tetranuclear clusters appears to be influenced by ligand substitution patterns and reaction conditions, highlighting key structural factors that control assembly of multinuclear Cu(I)–triazenido systems. Electrochemical studies, conducted in the absence and presence of acid, reveal substituent-dependent redox behavior across the series. Analysis of acid-free data demonstrates systematic modulation of Cu-centered redox processes by variations in ligand substitution, while proton-responsive current enhancement is observed under acidic conditions. These results establish structure–property relationships linking ligand substitution, nuclearity, and electronic properties in multinuclear Cu(I) complexes.
Abstract A series of gold(I) complexes featuring a novel ligand–gold–ynaminyl architecture was synthesized and characterized. The incorporation of a (carbazolyl)ethynide (C≡C-Cbz) ligand connects the photonic functionality of the carbazolyl with the N-heterocyclic carbene (NHC) through a long ethynide-Au bridge, showing shorter radiative lifetimes and higher ET values in solution in comparison to their carbene–metal–amido (CMA) congeners. The photophysical properties of the NHC complexes reveal a broad UV emission band when measured at room temperature and a hidden phosphorescence band with high quantum yield (up to 94%) at 77 K. This new photonic functional group based on polar ynamines is presented as a versatile platform for the design of high-energy gold-based luminophores with applications in photocatalysis.
Abstract Perovskite quantum dots (PeQDs) show promising potential in the optoelectronic field, but their commercial application is limited by the challenges of aqueous stability and large-scale production. Herein, we tackled both the issues via “one stone,” namely multidentate coordination strategy. This approach leverages 3-bromo-2-methylpropionic acid (BMPA), where the carboxyl and bromomethyl groups provide robust four-site anchoring to the surface Cs+ atoms. Experiments and theoretical calculations reveal such multidentate coordination could effectively passivate halide vacancies and suppresses defect formation. Each batch enables the production over 1.2 g BMPA PeQDs at production yield of >85% and low cost of ∼56 CNY/g, with no obvious emission shift and a near-unity photoluminescence quantum yield (PLQYs), demonstrating exceptional batch-to-batch consistency. Furthermore, the robust interface affords superior environmental resilience, with the PeQDs dispersion retaining approximately 50% of its photoluminescence (PL) after 960 h of storage at 25 °C. Finally, the white light-emitting diodes (LEDs), fabricated using these PeQDs, exhibit standard white emission with color coordinates of (0.33, 0.33), high color rendering index of 92.6, and significantly improved stability. This work underscores the potential of the multidentate strategy as a robust and efficient pathway for the commercial-scale manufacturing of aqueous PeQDs.
Abstract Systematic strategies for modulating trap distributions through B-site cation engineering in metal halide phosphors remain elusive. Here, we employ density functional theory to guide the isovalent substitution of Cd2+ with Zn2+ in Cs3Cd2Cl7:Sb3+ afterglow phosphors. By leveraging the electronegativity difference and ionic radius mismatch between Zn2+ and Cd2+, we perturb the local bonding environment while preserving the [SbCl6]3– emission framework. Zn2+ incorporation modifies the local structural and electronic environments, while thermoluminescence spectroscopy reveals a broadened trap distribution. The optimized composition, Cs3Cd1.95Zn0.05Cl7:0.04Sb3+, exhibits prolonged afterglow exceeding 180 s-substantially longer than that of the undoped counterpart, while maintaining green self-trapped exciton (STE) emission centered at 518 nm. These engineered defects enable multimode optical readout via thermal stimulation, 980 nm photostimulation, and X-ray excitation. This work establishes a clear correlation between B-site cation identity and defect energetics, providing actionable design principles for next-generation optical storage materials.
A new S = 1/2 d0 dioxorhenium complex, [Re(O)2(ap)(isq•)] ([ap]2- = 2,4-di-tert-butyl-6-(phenylamido)phenolate, [isq•]- = 2,4-di-tert-butyl-6-(phenylimino)semiquinonate), was prepared by oxidation of the Re(VII) species [Re(O)2(ap)2]-. Solid-state structural and spectroscopic data for [Re(O)2(ap)(isq•)] suggest a strengthening of the Re═O bonding upon oxidation of [Re(O)2(ap)2]-. [Re(O)2(ap)(isq•)] is a weak O-atom donor, H• acceptor, and modest outer-sphere 1e- oxidant, but it cleanly oxidizes the stable triphenylmethyl (Ph3C•) radical, affording Ph3COH and deoxygenated bimetallic μ-oxo dimers. Data support a mechanism of initial C-O radical coupling (RC) at a terminal Re═O bond, followed by net H• transfer from Gomberg's dimer, reversing the steps for classic rebound-type C-H hydroxylation. The closed-shell structural homologue [Re(O)2(ap)2]- has comparable O-atom transfer thermodynamics but is inert to Ph3C•. Computational data show the [isq•]- radical in [Re(O)2(ap)(isq•)] is partially delocalized into the closed-shell metal-oxo group in the ground state, which might permit the net 2e- oxo transfer to Ph3C• to occur via kinetically facile ligand-centered radical steps. Accordingly, a strategy is presented for the preparation of stable oxo-metal complexes that exhibit oxidizing oxyl radical-type reactivity via delocalization of a low-lying, redox-active ligand-centered hole into the terminal M-Ooxo π-bonding manifold. This "masked oxyl" approach establishes design principles for generation of thermodynamically stable oxidants that are kinetically activated for selective odd-electron bond-making and -breaking redox reactions, with broad implications for selective oxidations and energy conversion and storage.
Abstract Halide solid electrolytes are promising candidates for high-voltage all-solid-state batteries due to their high anodic stability. Here, we report the synthesis and characterization of lithium-containing halide solid electrolytes, Li2xAl1+xP1–xCl8, based on the recently identified orthorhombic Pbcm structure of AlPCl8. Among the nominal compositions characterized by PXRD (x = 0.15, 0.2, 0.333, and 0.5), the x = 0.15 and 0.20 phases retain the AlPCl8-derived framework as single-phase products. The materials were prepared via stoichiometric mechanochemical synthesis followed by low-temperature annealing. Structural analysis using joint Rietveld refinements of X-ray and neutron diffraction data confirmed distorted tetrahedral interstitial lithium sites that interconnect AlCl4 and (P/Al)Cl4 polyhedra. Bond-valence site energy calculations reveal crystallographically accessible Li+ migration pathways with low local migration barriers of ∼0.3 eV. The x = 0.20 composition exhibits an ionic conductivity of 6.3 × 10–7 S cm–1 at room temperature, with a negligible electronic conductivity of 1.9 × 10–10 S cm–1 and an apparent activation energy of ∼1.6 eV. Despite the modest ionic transport, linear sweep voltammetry indicates a high oxidation onset at ∼7.8 V vs In/In–Li, demonstrating high anodic stability among halide electrolytes. The large discrepancy between the calculated local barriers and the experimentally measured activation energy suggests that macroscopic Li+ transport is governed by factors beyond the intrinsic local hopping barrier. These results establish the AlPCl8-derived framework as a useful structural platform for exploring chloride-based Li+ conductors with accessible migration pathways and high oxidative stability.
Abstract Photocatalytic oxidation of hydrocarbons to carboxyl or carbonyl derivatives is considered a highly promising method, yet finding highly active and stable photocatalysts remains challenging. Herein, a decatungstate-based metal–organic framework (POMOF) photocatalyst, CuW10–DPNDI, engineered for efficient photocatalytic C–H bond activation, was prepared by incorporating [W10O32]4– as the photoactive component for HAT and SET, copper metal ions, and the photosensitizer ligand N,N’-bis(4-pyridylmethyl)naphthalenediimide (DPNDI). CuW10–DPNDI exhibits high photocatalytic activity for the oxidation of inert C(sp3)–H bonds under mild white-light irradiation. The coordination bonds between copper(I), DPNDI, and [W10O32]4–, hydrogen bonds, along with π···π stacking interactions, collectively enhance photoinduced electron–hole separation and facilitate charge transfer among components. The mechanism of C–H bond activation is mediated by [W10O32]4– anions via a HAT pathway, where the synergistic contribution of photosensitizer DPNDI and copper(I) enhances visible-light absorption and narrows the band gap. This work not only provides a sustainable strategy for C–H bond oxidation but also establishes POMOFs as robust platforms for advanced photocatalytic organic transformations.
Abstract Europium (Eu), characterized by its unique half-filled 4f electron shell, typically exhibits +2 and +3 oxidation states at ambient conditions and possesses a magnetic semiconducting phase. Here, using first-principles simulations, we systematically investigated the phase diagram, coordination environments, and magnetic properties of europium fluorides over a pressure range of 0–150 GPa. In addition to the known structures of EuF2 and EuF3, we discovered their high-pressure polymorphs with P63/mmc and Pmmn symmetries and further identified a novel F-rich phase EuF4 with the I4/m structure. Notably, both Pmmn-EuF3 and I4/m-EuF4 are predicted to feature rare 12-coordinate europium geometries, demonstrating hypercoordination behavior. Electronic structure calculations reveal that Pmmn-EuF3 is a ferromagnetic semiconductor, whereas I4/m-EuF4 exhibits ferrimagnetic half-metallicity. We further conducted complementary diamond-anvil-cell experiments to probe the structure evolution of EuF3 under high pressure. The predicted Pmmn-EuF3 was successfully synthesized at 45 GPa, as confirmed by in situ X-ray diffraction. Our findings provide insights into the pressure-induced evolution of the oxidation states and coordination environments of europium, serving as a useful reference for future studies on rare-earth metals under extreme conditions.
Abstract Coordinated water is a major obstacle in the design of high-performance energetic coordination complexes because inert aqua ligands lower energy density and suppress laser sensitivity. Herein, we report a simple strategy for removing coordinated water by changing the Cu:ligand (6-(1H-pyrazol-1-yl)-[1,2,4]triazolo[4,3-b][1,2,4,5]tetrazin-3-amine, APTTz) molar ratio from 1:1 to 5:1 during crystallization, which drives thermodynamic displacement of coordinated water by perchlorate anions. This yields hydrated ECP-1 ([Cu(APTTz)2(H2O)2](ClO4)2) with outer-sphere perchlorate at 1:1 and anhydrous ECP-2 ([Cu(APTTz)2(ClO4)2]) with inner-sphere perchlorate at 5:1. The structural transformation enhances laser initiation performance, with the ignition delay time and threshold both reduced by 58.6%. Both complexes reliably detonate HMX and penetrate 5 mm lead plates. Theoretical analysis reveals that water removal lowers crystal symmetry (P-1 → Pn), narrows the band gap (0.56 eV → 0.34 eV), and transforms the lowest-energy excitation from a symmetry-forbidden local excitation into a strongly allowed metal-to-ligand charge-transfer transition. Coordinated water is identified as a parasitic hole acceptor, while perchlorate acts as a structural enabler. This work reveals a trade-off between laser sensitivity and detonation performance, guiding the rational design of next-generation laser-ignitable energetic materials.
Abstract Broadband light-emitting hybrid perovskites are promising for solid-state lighting and display technologies, yet stable single-phase lead iodide hybrid perovskites combining intrinsic broadband emission with reversible chromaticity tuning remain scarce. Herein, we report the amino acid-based two-dimensional organic–inorganic lead iodide perovskite (l-cysH)PbI3·H2O, derived from l-cysteine, which exhibits reversible temperature-dependent emission-color tuning. The compound is a semiconductor with an optical band gap of 2.53 eV and displays dual-channel broadband photoluminescence across the visible region under UV excitation. Upon cooling from 238 to 78 K, the emission changes from yellowish-white (CIE: 0.342, 0.399) to a warmer, more saturated emission (CIE: 0.385, 0.473), while the integrated photoluminescence intensity increases approximately 27-fold. The emission comprises a narrow high-energy band attributed to free-exciton recombination and a broad lower-energy band tentatively assigned to self-trapped excitons. Arrhenius analysis yields an activation energy of 72.3(12) meV, indicating thermally activated quenching. Density functional theory calculations reveal an indirect fundamental band gap and strongly anisotropic charge transport, consistent with the layered structure. These results demonstrate thermally tunable broadband emission in a single-phase 2D amino acid-based lead iodide perovskite without halide mixing, extrinsic luminescent dopants, or multiphase engineering.
Abstract Controlling reactivity and pathway selectivity in N-heterocyclic silylenes (NHSi) and germylenes (NHGe) has lacked a unified mechanistic framework. Using density functional theory together with the activation strain model (ASM), energy decomposition analysis (EDA), and aromaticity metrics, we establish substrate deformation as the principal determinant of activation barriers across diazoalkane decomposition, alkyne functionalization, and small-molecule activation. Ring aromaticity, though measurable, predicts neither barrier heights nor pathway selectivity; instead, activation barriers scale with the geometric cost of distorting the incoming substrate to accommodate the larger Si and Ge centers. Excessive diazoalkane deformation, not ring distortion, drives the prohibitive C–H activation barriers, whereas the preferred N2-release pathway benefits from strong orbital interactions requiring little substrate reorganization. The paradigm holds across 5-ItBu and 5-Dipp frameworks and six-membered scaffolds (with pathway selectivity governed by deformation for the heavier congeners and by orbital interactions where deformation demands are comparable), and extends to Si–H, B–H, and C–F activation. N2-release yields a silene showing no Si═C bond cleavage over 2.6 ps of Born–Oppenheimer molecular dynamics (BOMD) up to 900 K, with low predicted barriers for PhOH, PhCCH, and NH3, providing a design framework for heavier-tetrylene reagents.
Abstract Zero-dimensional organic–inorganic hybrid zinc halides have emerged as promising lead-free candidates for blue-emitting optoelectronic devices due to their structurally tunable nature; however, their practical application is severely hindered by inherent optical inertness and unsatisfactory luminescence efficiency. Herein, a novel donor-π-acceptor (D-π-A) organic cation, 7-chloro-N-[2-(dimethylamino)ethyl]quinolin-4-amine (CDQI), is rationally designed, and a zero-dimensional (0D) hybrid zinc halide crystal (CDQI)(ZnCl4)·H2O is prepared via a facile solvothermal method. Notably, the crystal exhibits efficient broadband blue emission centered at 450 nm with a high photoluminescence quantum yield (PLQY) of 51.73%. Benefiting from the synergistic effect of hydrogen bonds and aromatic π–π stacking and the electronic transfer effect of the D-π-A structure, it also possesses excellent structural and optical stability in harsh environments. The assembled light-emitting diode achieves standard white-light emission with CIE coordinates of (0.31, 0.32) and a high color rendering index (CRI) of 92.8, long-term, stable luminescence, and linear, power-dependent emission. This work proposes an efficient D-π-A cation modulation strategy, offering a reliable guideline for developing high-performance lead-free blue-emitting hybrid halide optoelectronic materials.
Abstract We present the two-step synthesis of two new 2-naphthyl-substituted carbodiphosphoranes (CDPs). In the first step, either two equivalents of P(Naph)Ph2 (Naph = 2-naphthyl) and CH2Br2 or P(Naph)Ph2 and [Ph3P(CH2Br)]Br are reacted, whereby the symmetrical bis(phosphonium) salt 1a and the unsymmetric salt 1b are obtained. Subsequently, the CDPs 2a and 2b were prepared by deprotonation with two equivalents of potassium bis(trimethylsilyl)amide. After isolation, the coordination chemistry of 2a and 2b toward CuCl is explored where, depending on the stoichiometries of the starting materials, mononuclear (3a and 3b) and dinuclear compounds (4a and 4b) are obtained. All prepared compounds were characterized by NMR spectroscopy, mass spectrometry, and elemental analysis, and for 1a/b, 2a, 3b, and 4a/b, single crystals suitable for X-ray diffraction studies could be obtained. Furthermore, the photophysical properties of the 2-naphthyl-substituted CDPs 2a/b and their corresponding CuI complexes 3a/b and 4a/b have been investigated by steady-state and time-resolved luminescence studies at room temperature and at 77 K in various aggregation states, and further insight is provided by DFT/TD-DFT calculations. While 2a/b display features of thermally activated delayed fluorescence (TADF), 3a/b and 4a/b exhibit a much more complex excited-state behavior due to the interplay of metal-to-ligand charge transfer (MLCT) and naphthyl ligand-centered (LC) states, resulting in multiple simultaneous luminescence phenomena involving TADF, 1LC, and 3LC emission.
Abstract Three rare-earth-embedded phosphotungstates with a dimeric sandwich structure containing two types of building blocks (BBs) [NH2(CH3)2]11H[RE(P2W17O61)(W5O18H)]·9H2O [RE = Dy3+ (1), Er3+ (2), Pr3+ (3)] have been synthesized via a one-pot self-assembly strategy. A distinctive feature is that the polyanion [Dy(P2W17O61)(W5O18H)]12– was composed of one monolacunary Dawson [P2W17O61]10– and one monolacunary Lindqvist [W5O18]5– segments. To the best of our knowledge, this is the first successful synthesis of a rare-earth-embedded polyoxotungstate incorporating both Dawson-type and Lindqvist-type BBs. In the presence of compounds 1–3, the oxidation of benzyl alcohol (0.5 mmol) to benzaldehyde was accomplished using H2O2 as a green oxidant. Notably, within 9.5 h, conversions of 99.5, 98.3, and 93.6% and selectivities of 97.3, 99.5, and 92.5% were obtained, respectively. A plausible reaction mechanism is proposed and verified by radical quenching experiments and electron paramagnetic resonance (EPR) trapping experiments. The results indicate that these compounds can effectively activate H2O2 to generate singlet oxygen (1O2), thereby achieving the selective oxidation of benzyl alcohol to benzaldehyde.
Abstract A series of cationic gold(I) complexes of the type [Au(PPh3)(Ar-Bian)](CF3SO3) based on 1,2-bis[(2,4,6-trimethylphenyl)imino]acenaphthene (tmp-Bian), 1,2-bis[(4-chlorophenyl)imino]acenaphthene (4–Cl-C6H4–Bian), 1,2-bis[(4-bromophenyl)imino]acenaphthene (4–Br-C6H4–Bian), and 1,2-bis[(4-iodophenyl)imino]acenaphthene (4–I-C6H4–Bian) were prepared. All complexes were fully characterized by spectrochemical methods, and their crystal structures were established by X-ray diffraction analysis. The electrochemical behavior of all complexes was studied by using cyclic voltammetry. The stability of the complexes in solution was investigated using 1H NMR and UV–vis spectroscopies. The anticancer activity of Au(I) complexes was evaluated against a panel of cell lines in comparison with free 1,2-bis(arylimino)aceaphthenes (Ar-Bian) and initial [Au(PPh3)Cl]. All complexes were cytotoxic in a low micromolar range and showed selectivity toward cancer cells in comparison with MRC-5 human lung fibroblasts. The ability of the complexes to bind DNA and BSA was investigated by spectroscopic methods, molecular docking, and molecular dynamics studies. The DNA-damaging activity of gold(I) complexes was evaluated in MCF-7 cells using the comet assay. Reactive oxygen species production in MCF-7 cells was studied using confocal microscopy. The lipophilicity of complexes was determined using the n-octanol/water shake-flask method. Determination of the cell death pathway was performed using an Annexin-5-FITC/PI double staining test followed by fluorescence-activated cell sorting (FACS) analysis.
Abstract The electronic properties of a suite of di- and trinuclear ruthenium bis(acetylide)-based complexes incorporating phenylene and naphthylene bridges have been explored experimentally and computationally. The complexes, [{trans-Ru(dmpe)2(C≡CtBu)}2(μ2-C≡C(2,6-C10H6)C≡C)], [{trans-Ru(dmpe)2(C≡CtBu)}2(μ2-C≡C(2,7-C10H6)C≡C)], and [{trans-Ru(dmpe)2(C≡CtBu)}3(μ3-(C≡C)3(1,3,5C6H3)], were formed via the metathesis of terminal organic bisacetylenes with the methylruthenium complex, [trans-Ru(dmpe)2(CH3)(C≡CtBu)], in the presence of methanol and under mild conditions. Spectroelectrochemical analyses of these species showed that the linearly π-conjugated 2,6-naphthylene bridge enabled better electronic communication between redox-active ruthenium-acetylide sites than the cross-conjugated 2,7-naphthylene bridge.
Abstract Crystal structure prediction (CSP) is a cornerstone technology for the efficient discovery and rational design of functional materials. Here, we propose a deep-learning-enabled dual-mode CSP framework that simultaneously supports two complementary tasks: predicting stable crystal structures for given elemental compositions and identifying chemically viable elemental substitutions for a predefined crystal topology. The framework employs an improved normalized structural fingerprint descriptor that integrates local coordination topology without global spatial-scale information. A cascaded site-probability model, composed of an autoencoder and sigmoid-based classifiers, is developed to predict the occupancy probabilities of 84 chemical elements at crystallographically distinct sites and to efficiently rank candidate structures accordingly. Remarkably, even when trained solely on topological information, the model autonomously captures elemental chemical similarity and intrinsic periodic trends, yielding chemically meaningful multielement probability distributions. Application of the proposed framework to high-throughput screening of superhard materials in the B–N system successfully identifies a thermodynamically, mechanically, and dynamically stable hexagonal BN phase, together with a metastable monoclinic B2N3 structure. Furthermore, elemental substitution screening on the zinc-blende prototype reveals two metastable compounds, In4Sb4 and Ga4Sb4. The proposed framework provides a low-cost, high-efficiency, data-driven strategy for the rapid discovery of inorganic materials.
Abstract Schottky junctions are widely used to suppress charge recombination in photocatalysis, but their efficiency is often constrained by weak solar energy utilization, high interfacial resistance, and sluggish surface reaction kinetics. Plasmonic photocatalysis, driven by localized surface plasmon resonance (LSPR), offers a compelling route to simultaneously enhance light absorption, charge separation, and enable in situ photothermal heating. Here, we rationally design a plasmonic MoO2/ZnIn2S4 Schottky junction with well-defined interfacial Mo–S bonds and pronounced LSPR characteristics. These interfacial chemical bonds serve as efficient atomic-scale bridges to lower the interfacial barrier, thereby accelerating charge carrier transfer and separation. Meanwhile, the LSPR-induced photothermal effect significantly boosting surface reaction kinetics. The optimized 10-MO/ZIS achieves remarkable hydrogen evolution rates of 3.58 mmol·g–1·h–1 under visible light irradiation, corresponding to 11.9-fold enhancements over pristine ZnIn2S4. Notably, the apparent activation energy is substantially reduced from 42.4 to 25.9 kJ mol–1. Mechanistic studies reveal that the synergy between Mo–S bond-facilitated charge transport and LSPR-driven local heating is pivotal to the enhanced performance. This work establishes a new paradigm for integrating plasmonic effects with Schottky junctions to concurrently optimize charge dynamics and reaction kinetic for advanced solar fuel production.
