Journal of Colloid and Interface Science最新文献

Utilizing the thermodynamically favorable urea oxidation reaction (UOR) as a substitute for the oxygen evolution reaction (OER) in conventional water electrolysis offers a viable method for wastewater treatment and energy-efficient hydrogen generation. A series of samples with abundant cation vacancies were synthesized via a hydrothermal method followed by alkaline etching. The electronic and crystal structures of the catalysts were simultaneously modulated by precisely tuning the concentration of the vacancy-inducing medium. The β-type NiCo_v 1:1-2% with abundant cation vacancies demonstrates superior UOR activity, with just 1.31 and 1.35 V vs. RHE needed to reach current densities of 10 and 100 mA cm^-2, respectively. Characterization experiments indicate that the optimization of electronic structure through cation vacancies and distinctive multilayered flake morphology can enhance the number of active sites and improve mass transfer efficiency. A series of in situ measurements further corroborate the rapid yet moderate phase transitions of NiCo_v 1:1-2%. Theoretical calculations demonstrate that the introduction of cation vacancies optimizes the balance between reactant adsorption and product desorption, leading to a reduced Gibbs free energy barrier for the rate-determining step of UOR. This study offers valuable guidance for the rational design of efficient and versatile catalysts for small-molecule oxidation reactions.

The development of efficient photocatalysts for carbon‑nitrogen (CN) bond formation from aldehydes is highly desirable for the synthesis of functional organic molecules but remains a significant challenge. Herein, we report a novel imidazobenzothiadiazole-based tricarboxylate compound (H₂Ph-COOH, defined as "T-shaped" ligand), and successfully construct the first single-component metal-organic frameworks (MOFs, UiO-68-Ph-COOH) featuring an exposed carboxyl group. This MOFs was effectively employed in the photocatalytic synthesis of amides from aldehydes and amines. The carboxylated T-shaped ligand-based UiO-68-Ph-COOH exhibits outstanding optoelectronic properties and exceptional photocatalytic activity for amide synthesis at room temperature, achieving high yields (up to 92%) within 12 h, along with long-term durability and excellent stability. In comparison, control MOFs (UiO-68-Bt and UiO-68-Ph) derived from linear ligands showed markedly lower catalytic activity (10% and 16% yields, respectively) under identical reaction conditions. Mechanistic studies reveal that the exposed -COOH groups in UiO-68-Ph-COOH act as Brønsted acid sites, which promote the formation of key amino alcohol intermediate and concurrently facilitate the generation of superoxide radical (O₂^•-). This synergistic effect significantly improves the photocatalytic efficiency for amide synthesis. Additionally, UiO-68-Ph-COOH efficiently catalyzes the formation of benzothiazoles and benzimidazoles (up to 94% yield within 1.5 h). This work provides the first demonstration that a single-component MOFs can independently drive photocatalytic amide synthesis and reveals the exposed -COOH functionalization as a crucial design strategy for MOFs-based photocatalysts, thereby opening new avenues for designing efficient MOFs-based photocatalysis of CN bond formation.

Oxygen evolution and reduction reactions (OER/ORR) are fundamental to energy conversion technologies such as water electrolyzers and fuel cells. However, the intrinsic linear scaling relationship (LSR) between the intermediate adsorption energies limits catalytic activity. Overcoming this limitation could surpass the conventional activity-volcano relationship and unlock high-performance OER/ORR electrocatalysts. Herein, we propose a novel interlayer-confinement engineering strategy, utilizing spatially confined dual active sites in interlayer-confined dual single-atom-catalysts (iDSACs), to fundamentally break the intrinsic LSR by simultaneously manipulating reaction pathways and intermediate adsorption. Density functional theory (DFT) computations demonstrate that the synergistic space-electron effects enhance charge transfer, activate the O-O bond, and facilitate its dissociation. Further, tuning the confinement strength exerts opposing effects on various intermediates and catalysts. Consequently, this strategy effectively disrupts the LSR between *OOH and *OH adsorption, thereby improving OER and ORR activities. Additionally, an optimal interlayer distance of 7.0 Å is identified to balance dual-site synergy and steric effects, achieving low overpotentials (0.26 V for OER and 0.30 V for ORR on IrN₄). This work establishes space-electron synergy as a generic platform to disrupt adsorption scaling laws, advancing efficient electrocatalyst design and providing fundamental insights into confined electrocatalysis.

The amorphous nickel (oxy)hydroxides (NiO_x(OH)_y) with enriched oxygen vacancies (O_v) grown on the surface of Ni₃S₂ substrate were designed to boost oxygen evolution reaction (OER) activity. The achieved electrocatalysts showed excellent OER performance with η_j10 of 130 mV, η_j100 of 256 mV, and stability for at least 375 h, outperforming the commercial RuO₂ catalysts and most of the state-of-the-art OER catalysts. A new universal stoichiometric mismatch method was developed to synthesize this special structure-by etching low-sulfur-content sulfides in an alkaline aqueous environment to guide the formation of oxygen-deficient amorphous metal oxides. Further, to obtain well-direction low-sulfur nickel sulfide, a novel reverse epitaxial growth method was developed. In this method, in-situ prepared [001]- direction nano Bi₂S₃ needles were deposited on nickel foam, guiding the substrate to transform into [001]-direction Ni₃S₂ while causing Bi to detach from the surface. Here, the as-obtained amorphous oxygen-deficient material effectively activates lattice oxygen, and the oxygen vacancies along with the amorphous character at the Ni₃S₂-NiO_x(OH)_y interface trigger a unique charge transfer effect, fully activating the surface to promote OER.

Surface ligands are crucial for perovskite quantum dot (PQD) optoelectronics. However, long alkyl chains limit charge transport, while short chains destabilize their soft lattice, presenting a stability-mobility dilemma. Moreover, surface-bound protonated primary amines are susceptible to deprotonation, accelerating performance decay and structural collapse. In this work, we introduced tetrabutylphosphonium bromide (TBPB) as a surface passivation ligand to overcome these limitations. TBPB combines minimal molecular polarity-enabling a short chain for superior charge transport-with a fully coordinated phosphonium center that resists deprotonation and passivates halogen vacancies. This yields quantum dots with near-unity PLQY and robust stability, leading to LEDs achieving a maximum external quantum efficiency (EQE) of 24.28% and luminance of 122,786 cd m^-2, far surpassing control devices. Further shortening the ligand chain increases EQE to 27.89% but at the cost of severe luminance loss, underscoring the delicate balance in ligand engineering.

Silicon luminescence remains a significant challenge, and its origin is intense debate ever since. Here we show, for the first time, a luminescent strategy involving silicon nanorods coupled with plasmonic gold nanopore arrays. It is demonstrated that the luminescence intensity of silicon nanorods induced by plasmonic gold nanopore arrays is nine times higher than that of pure silicon nanorod samples. Despite the absence of an insulating spacer between the gold nanopore arrays and silicon nanorods, no luminescence quenching is observed. Furthermore, we employ finite difference time domain simulations to map the electric field distribution and estimate a Purcell factor of 5, which is lower than the experimentally measured luminescence enhancement. This indicates that the observed luminescence enhancement is only partially attributable to the Purcell effect. Importantly, the Purcell effect would not cause a shift in the luminescence peak, whereas a significant peak shift is observed in our experiments. Based on these facts, a novel luminescence mechanism is proposed to complementally account for the remarkable luminescence enhancement observed in our experiments. Plasmonic gold nanopore arrays-induced energy level splitting may appear in silicon nanorods, which generates a localized direct bandgap, thereby yielding enhanced visible light emission.

The design of functional materials with increasing entropy has become a hot field in recent years. Motivated by the traditional concept of high entropy (HE), the anionic doping with multiple heteroelements towards increasing entropy has been considered to be a new clue to design highly efficient catalysts. In present work, we report the design of a non-metallic anion high-entropy (AHE) codoped hollow carbon nanocage as an oxygen catalyst for Zn-air batteries (ZAB). A series of non-metallic heteroatoms, including nitrogen (N), phosphorus (P), sulfur (S), boron (B), and fluorin (F), are employed as anionic dopants to construct the AHE codoped carbon nanocages. The influences of AHE engineering on the electrocatalytic behaviors of the hollow carbon nanocages in the oxygen reactions are explored. Through synergistic modulations on anionic doping engineering and structure design, the AHE doped hollow carbon nanocages achieve the superior oxygen reduction reaction (ORR) activities and faster kinetics in comparison to the counterparts of anionic medium-entropy (AME, e. g. N, P, S, B), anionic low-entropy (ALE, e. g. N, P, S, or N, P/S, or N) doped and undoped samples. Density functional theory (DFT) calculations reveal that the AHE engineering regulates the electronic structure, adjust the energy barrier, and modulate oxygen intermediates adsorption capability, which synergistically accelerate the ORR behaviors. In addition, the full ZAB battery integrated with the AHE codoped hollow carbon nanocages cathode delivers the high power density (212.1 W kg^-1) and long cycle life (500 h cycling). More impressively, the solid-state ZAB with the hydrogel electrolyte and AHE doped carbon nanocage cathode shows the good flexibility and high adaptation in a wide temperature range. Therefore, this work not only introduces a synergistic modulation strategy to optimize the anion high-entropy catalysts for oxygen catalysis, but also promotes the fast development of high-performance ZAB towards different working conditions.

Halloysite nanotubes (HNTs), naturally occurring aluminosilicates with a tubular structure, are promising nanocarriers for drug delivery due to their biocompatibility and unique morphology. However, their interaction with lipid membranes remains not fully explored. In this work, we aim at elucidating on the adhesion of HNTs on unilamellar vesicles made of phospholipids used as model of biological membranes. The adhesion was modulated by varying the lipid composition, ionic strength, and the size ratio between HNTs and vesicles. The adhesion mechanism was also studied by trapping a single HNT with optical tweezers and let it interact with a single vesicle. These findings show a preferential adhesion of the HNT tip on the lipid bilayer, which represents an important step toward directional membrane targeting in biomedical applications.

Rational design and synthesis of stable and efficient photocatalysts for selective U(VI) capture in water remains a great challenge due to the complicated water environment. Herein, considering the synergistic interaction between anthraquinone (-AQ, electron acceptor) and methoxy (-OCH₃, electron donor), a series of ternary donor-acceptor-acceptor (D-A1-A2) covalent triazine frameworks named as OCH₃(x)-AQ(y) (x and y represent different content ratios) were rationally designed and synthesized via molecular regulation. This work not only constructed a directional charge-transfer pathway, but also greatly improved the utilization efficiency of photogenerated electrons in OCH₃(x)-AQ(y) framework, which was also further verified by density functional theory (DFT) calculations. Finally, OCH₃(2)-AQ(3) could reach nearly 100% removal efficiency of U(VI) within 240 min under visible light irradiation in air. Meanwhile, OCH₃(2)-AQ(3) showed an extremely high distribution coefficient (K_d, 1.07 × 10⁶ mL·g^-1) for U(VI) under multicomponent ion competition and further performed high removal efficiencies (>98%) in real water environments, such as seawater and groundwater. Importantly, the machine learning results also demonstrated that the structural characteristics would greatly influence the catalytic performance of CTF catalysts. The component tuning of donor-acceptor groups achieved synergistic effects in stepwise charge transport and target-selective site accessibility, which offered an effective photocatalytic strategy for U(VI) extraction in complex water environment.