Journal of Colloid and Interface Science最新文献

The development of efficient photocatalysts for solar-driven hydrogen production is crucial for addressing energy and environmental challenges. Herein, a full-spectrum responsive "dual-engine" photocatalytic system based on a multifunctional cocatalyst featuring electrons extraction, photothermal heating effect and abundant active sites was successfully designed. In this system, hierarchical NiCo₂S₄ (NCS)/defective ZnCdS (ZCS-Vs) composite photocatalysts were synthesized through a simple physical mixing method with hierarchical NCS modified ZCS-Vs nanoparticles. Owing to the introduction of black hierarchical NCS, these composite photocatalysts show a wide light absorption range from 300 to 1200 nm due to the introduction of black hierarchical NCS. Under broad-spectrum illumination, the optimized photocatalyst delivered a maximum H₂ production rate of 22.19 mmol·g^-1·h^-1 and an apparent quantum yield of 6.29 % at 420 nm, corresponding to roughly a 42-fold improvement over pure ZCS-Vs. This outstanding H₂ evolution performance originates from three key factors. First, the metallic nature and high work function of NCS enable the formation of a Schottky junction with ZCS-Vs, which efficiently extracts photogenerated electrons from ZCS-Vs for the reduction of H⁺ ions. Second, under photoexcitation, NCS exhibits a strong localized surface plasmon resonance (LSPR) effect, leading to a rapid increase in local temperature on the catalyst surface. This localized heating further elevates the overall reaction solution temperature, thereby reducing the energy barrier for photocatalytic H₂ evolution. Third, 3D hierarchical structure of NCS not only inhibits nanoparticle aggregation and provides abundant active sites, but also enhances light harvesting through internal scattering, thereby maximizing both charge separation and photothermal efficiency. Consequently, this "dual-engine" photocatalytic system provides a feasible pathway for designing photothermal-assisted composite photocatalysts to enhance photocatalytic H₂ evolution efficiency.

Ruthenium-based materials are widely regarded as promising electrocatalysts for water splitting, owing to their platinum-like electronic characteristics and favorable binding energies with reaction intermediates. Nevertheless, the oxidation behavior of ruthenium at elevated potentials induces structural degradation, precipitating the dissolution of active species and thereby undermining stability during the oxygen evolution reaction (OER) in acidic media. Herein, we reported a novel RuO₂@Ru heterostructured catalyst with cobalt and copper co-doping (Co, Cu-RuO₂@Ru) for stable acidic water electrolysis. The heterostructured catalyst exhibited exceptional performance, attaining an ultralow overpotential of 182 mV at 10 mA cm^-2 for the OER and a low overpotential of 217 mV at 250 mA cm^-2 for the hydrogen evolution reaction (HER), surpassing the benchmark Pt/C catalyst. Electronic-structure analyses indicated that the RuO₂@Ru heterointerface promoted charge redistribution following Co and Cu co-doping, effectively reducing the oxidation state of ruthenium within RuO₂ and yielding an electron-deficient metallic Ru phase. Moreover, mechanistic investigations revealed that electron transfer induced by Co and Cu co-doping optimizes the adsorption and desorption kinetics of hydrogen and oxygenated intermediates, thereby accelerating the reaction kinetics of both HER and OER in acidic media, ultimately leading to exceptional overall water splitting performance.

Realizing Zn metal anodes with long lifespan performance is a prerequisite for the commercialization of Zn-ion batteries, which is limited by severe water erosion, side reactions and dendrite formation. Herein, a series of hydrophilic metalloporphyrin coatings were employed to stabilize the Zn anode by screening their central metal sites from Mn to Zn. Among them, central copper (Cu²⁺) site significantly blocks the competitive hydrogen evolution reaction (HER) by elevating the adsorption barrier for the hydrogen proton intermediate (H*), suppressing both Heyrovsky and Tafel steps. Consequently, the HER overpotential of CuTCPP@Zn is increased while parasitic side reactions are reduced. Furthermore, the enhanced zincophilicity of CuTCPP@Zn facilitates a high Zn²⁺ transfer number of 0.70, which promotes uniform nucleation and deposition. As a result, CuTCPP@Zn delivers a stable cycling life exceeding 1460 h at 1 mA cm^-2 and 453 h even at 5 mA cm^-2. This work provides insights for precisely altering intrinsic HER activity by regulating central metal sites of hydrophilic metalloporphyrin coatings from a thermodynamic perspective, thereby realizing the construction of stable Zn metal anodes.

Hypothesis: The newly synthesized amphiphilic tadpole bottlebrush copolymer can exist in solution as unimers (disassembled polymer chains) or micelles depending on pH. Owing to this specific structure, these assemblies are at thermodynamic equilibrium, allowing for dynamic transitions between unimer and aggregated states. We hypothesize that the same copolymer can stabilize emulsions with distinct properties at varying pH, whether in its unimer or micellar state (Pickering emulsions).

Experiments: We characterized the copolymer behavior in aqueous solutions across pH range using dynamic light scattering (DLS), contact angle measurements, and dynamic tensiometry. Dodecane-in-water emulsions were prepared using the copolymer at various pH values. Emulsion characteristics were studied using optical microscopy and laser granulometry, complemented by visual observations to assess stability over time. The adsorption of polymer micelles at the emulsion droplet surface was investigated using transmission electron microscopy (TEM) of freeze-fractured samples.

Findings: Above pH 5-6, the copolymer acts as a macromolecular surfactant, resulting in emulsions with short-term stability. At lower pH (pH <5-6), when the copolymer self-assembles into micelles, very stable emulsions are obtained, exhibiting long-term stability (> 2 years) even at low copolymer concentrations (as low as 0.001 wt% with respect to total sample weight). Drop size is tunable with the copolymer concentration. TEM analysis of freeze-fractured emulsions reveals micelle adsorption at the droplet surface at low pH, highlighting their efficiency as Pickering emulsion stabilizers. Despite the copolymer reversible assembly in solution, no emulsion breakup occurs when pH increases to reach the unimer state domain. This unexpected behavior suggests that adsorbed copolymer micelles lose pH-sensitivity at the water-dodecane interface, demonstrating a unique system where interfacial behavior differs from solution behavior.

Electrode-electrolyte interfaces are of paramount significance in solid-state batteries. However, the enhancement of lithium (Li) conduction and the mitigation of Li dendrite formation constitute a dual challenge to interfacial structural design, as conventional rigid interfaces fail to balance ionic mobility and mechanical blocking. Herein, we report a biomimetic soft-hard-soft hierarchical architecture as an interfacial transition layer between the anode and solid electrolyte. Breaking from conventional rigid designs, this architecture leverages synergistic layer interactions to redistribute interfacial stress: the soft layer's electrospun network establishes 3D ion-transport pathways that accelerate Li⁺ conduction, while the poly(vinylidene fluoride) (PVDF) hard layer-mechanically reinforced by the underlying soft substrate-simultaneously suppresses dendrite penetration and enhances structural integrity. Consequently, the hierarchical structure achieves a tensile strength of 49.2 ± 2.1 MPa (n = 3) MPa, an electrochemical window of 5.20 ± 0.08 V (n = 3), and an ionic conductivity of (2.82 ± 0.09) × 10^-4 S cm^-1 (n = 3) cm^-1 at 25 °C. This performance directly enables high-performance cycling in LiFePO₄ || Li cells 136.3 ± 2.8 mAh g^-1 (n = 3) at 1.0C, 93.8 ± 0.8% (n = 3) capacity retention after 200 cycles, 99.5 ± 0.3% (n = 3) coulombic efficiency). The ionic conductivity and interfacial stability of the novel interface are significantly superior to those of commercial solid-state electrolyte films. This study highlights the potential of the bio-inspired spatial gradient electrolyte to simultaneously enhance Li⁺ conductivity and mitigate dendrite formation.

The development of practical lithium (Li) metal battery (LMB) is severely restricted by the poor stability of electrode-electrolyte interfaces (EEIs) and sluggish interfacial kinetics. Modulating Li-ion solvation structure is critical for addressing this issue, but remains challenging. Herein, we propose a novel strategy of incorporating multiple anions and functional solvent to tailor a unique anion-enriched and fluoroethylene carbonate (FEC) coordinated weak solvation structure for interfacial-stable high-performance LMBs. Theoretical calculations and experimental results indicate that the first Li-ion solvation sheath is dominated by multiple anions and FEC molecules, leading to a largely diminished coordination of Li⁺-solvents and an accelerated interfacial dynamics. Simultaneously, inorganic-rich robust EEIs are further constructed via the preferential redox decomposition of the solvated anions and FEC molecules, achieving a remarkable interfacial stability and dendrite-free Li plating/stripping behavior. Consequently, the symmetric Li||Li cells realize an ultra-long stable cycle of 5400 h at 2 mAh cm^-2, and the Li||LiFePO₄ (LFP) full cells demonstrate an excellent rate and cycling performance even under high LFP-loading, relatively low negative/positive capacity ratio (N/P) and less electrolyte usage. Our findings reveal a facile proposal to precisely tailor weak Li-ion solvation structure by integrating anion chemistry and functional solvent, paving the way for advanced electrolyte design and high-performance LMBs development.

Conventional solvent-free nanofluids hold promise as lubricants but often face challenges in intricate preparation and unadjustable performance. Herein, we developed a facile one-pot strategy for synthesizing MoS₂ quantum dots (QDs) nanofluids (MoNFs) via a coordination-confined growth approach, which features cyan-fluorescent with an average size of 3.8 nm, homogeneously dispersed in a tailored ionic liquid matrix. The resulting MoNFs exhibit tunable viscosity and desirable shear-thinning behavior. When evaluated as lubricants, the optimal formulation (3MoNFs) decreases wear volume by 73.8% compared to the base fluid. Comprehensive characterization of worn track reveals a triplex synergistic lubrication integrating an electric-double-layer film, tribochemical reaction film and solid-like nanofluid layer, concurrently assisted with repairing pre-existing wear scars. Impressively, blending merely 0.7 wt% 3MoNFs into commercial SN 0 W-30 engine oil enhances its anti-wear performance by 47.5%, demonstrating outstanding potential for high-performance lubricants.

Per- and polyfluoroalkyl substances (PFAS) are persistent and toxic water pollutants that pose significant environmental and health risks. Various methods exist for PFAS treatment, most of which rely on adsorption. However, these methods often produce byproducts that require additional treatment before disposal. Here we show a facile method for degrading model pollutants perfluorooctanoic acid (PFOA) and trifluoroacetic acid (TFA) using a low energy IR CO₂ laser on a laser-induced graphene (LIG) substrate, with NaOH serving as a mineralizing reagent. Laser treatment achieved up to 68% mineralization and the conversion of strong CF bonds present in PFOA into inorganic fluoride (NaF) was observed depending on the laser power, with optimum performance at 8% power. The fluorine mineralization efficiency increased with a larger Na-to-F molar ratio, up to a ratio of 4.5. Additionally, the LIG substrate was reusable for up to five treatment cycles under the optimal laser power. The method was also applied to a more volatile short chain perfluoroalkyl carboxylate TFA, and up to ∼27% of the organic fluorine was converted to NaF as quantified by ion chromatography. Contact angle measurements for both PFOA- and TFA-treated LIG showed decreased wettability after laser irradiation compared to deionized water (DI)-treated controls, possibly indicating incorporation of fluorine (CF) into the LIG chemical structure surface during degradation. The low cost of the methodology and reuse of the substrate offers a sustainable alternative for PFAS degradation and mineralization that might be incorporated into advanced water purification technologies.

Triple-negative breast cancer (TNBC), lacking effective therapeutic targets, is highly aggressive, prone to metastasis, and associated with poor prognosis, highlighting the necessity for innovative therapeutic strategies. Ferroptosis, an emerging form of iron-dependent programmed cell death, presents a promising treatment approach. However, its effectiveness is often hindered by adaptive resistance within the tumor microenvironment and inefficient drug delivery. To address these limitations, the glutathione (GSH)-responsive disulfide linker (-SS-) was utilized to engineer rhein (Rhe, chemotherapeutic agent) and ferrocene (Fc, ferroptosis booster) into the self-assembling small-molecule prodrug RSSF. Sorafenib (SOR), a ferroptosis inducer, was stably loaded into RSSF via a simple nanoprecipitation method, yielding the newly nanoprodrug designated as SOR@RSSF nanoparticles (NPs) for the combination therapy of TNBC. SOR@RSSF NPs exhibit markedly enhanced cellular uptake and enable the highly specific and synchronous release of Rhe, Fc, and SOR in response to intracellular GSH levels. Notably, Fc efficiently generates hydroxyl radicals (•OH) through the Fenton reaction, thereby inducing pronounced oxidative stress, while SOR concurrently impaired the cellular ferroptosis defense machinery. Combined with the chemotherapeutic activity of Rhe, the resulting lipid peroxide (LPO) accumulation and GSH depletion synergistically trigger both ferroptosis and apoptosis selectively in tumor cells. In a 4T1 tumor-bearing mouse model, SOR@RSSF NPs significantly inhibited tumor progression while maintaining a favorable biosafety profile. Overall, this study presents a promising ferroptosis-sensitizing strategy using a nanoprodrug delivery system for combination therapy against TNBC.