Journal of Colloid and Interface Science最新文献

Unraveling the reaction mechanism of the electrochemical CO₂ reduction reaction (CO₂RR) is a cornerstone in the quest for high-performance catalysts. This work adopts S-doped NiN₄ (NiN₃S₁) as a probe to reveal the synergistic promotion of local coordination and the reaction microenvironment on CO₂RR. The results show that N, S-coordination decreases the required potential for CO₂ chemical adsorption from -0.54 to -0.23 V. An explicit water-assisted mechanism for CO₂ activation is demonstrated, where H₂O molecules act as proton donors and form hydrogen-bond networks to facilitate CO₂ activation and reduce the reaction energy for *COOH formation. The applied potential (U) vs. Standard Hydrogen Electrode (SHE) promotes electron transfer and proton-coupled processes, thus improving the intermediate adsorption and reaction activity. As a result, the limiting potential of CO₂RR to CO decreases from -1.38 to -0.48 V with the increase in applied potential (U) vs. SHE from 0 to -0.84 V. Hydrogen evolution reaction on NiN₃S₁ is investigated as well to reflect the high CO₂RR selectivity. The results of this work highlight the synergistic promotion of coordination environment, explicit water molecules, and applied potential (U) vs. SHE to efficient CO₂RR, providing theoretical guidance for designing advanced CO₂RR electrocatalysts.

The integration of photothermal therapy (PTT), photodynamic therapy (PDT), and immunotherapy represents a promising strategy for enhancing anticancer efficacy. However, current approaches often rely on cocktail-based nanoplatforms that load multiple agents, which complicates preparation and raises concerns about stability and potential side effects. Therefore, developing structurally simple, easily synthesized nanomaterials with inherent multifunctionality is highly desirable. In this work, we report the first synthesis of biocompatible heterostructures. The interfacial contact within these heterostructures facilitates efficient charge carrier separation, enabling the simultaneous activation of photothermal conversion and photodynamic functionalities under near-infrared (NIR) irradiation. Beyond these photophysical effects, the obtained Bi₂Se₃@BiSe nanosheets effectively polarize M0 macrophages toward the tumor-suppressive M1 phenotype, a process which in turn promotes robust immunogenic cell death. Collectively, this work establishes Bi₂Se₃@BiSe as a versatile nanoplatform for triple-modal cancer therapy, seamlessly integrating PTT, PDT, and immunotherapy, thus proposing a novel paradigm for developing next-generation combinatory cancer therapeutics.

Covalent organic frameworks (COFs) exhibit considerable promise as lithium-ion battery anode materials due to their structural design flexibility and high theoretical capacities. However, critical challenges persist, including low electrical conductivity, structural instability arising from reversible bond cleavage, and inefficient utilization of electrochemically active sites. This study employs a stable dioxane-linked COF (DOL-COF) in terms of structure as the anode material and implements an interfacial engineering strategy to address these limitations. The approach enables orientation-designed and π-π interaction-driven in-situ growth of DOL-COF nanosheets on reduced graphene oxide (rGO) scaffolds. Electrochemical analysis identifies inefficient charge-mass transport within DOL-COF as the primary kinetic bottleneck. Theoretical calculations elucidate charge transport characteristics and reveal a tripartite lithium storage mechanism in DOL-COF, comprising Faradaic intercalation, pseudocapacitive redox storage, and non-Faradaic capacitive storage. This mechanistic insight guides the optimization of charge-mass transport via interfacial engineering. The resultant DOL-CRG-60 nanocomposite achieves electrode-mass-based reversible capacities of 1289 mAh g^-1 at 0.1 A g^-1 and 291 mAh g^-1 at 5.0 A g^-1, with 94.5% capacity retention after 3000 cycles at 5.0 A g^-1. The DOL-CRG-60 nanocomposite delivers an effective specific capacity of 1425 mAh g^-1, corresponding to approximately 84.5% utilization of Faradaic active sites. These enhancements originate from synergistic optimization of electronic conductivity, ion/electron transport pathways, and active-site accessibility, as evidenced by comparative electrochemical analyses. This work demonstrates that strategic manipulation of interfacial electronic structures and nanoscale architecture provides a viable approach for developing high-performance organic electrode materials with potential for diverse energy storage applications.

Interfacial effects critically regulate photocatalytic pathways through charge transfer modulation, reactant enrichment, and transition-state stabilization. However, precisely manipulating free electrons to drive efficient O₂ reduction to H₂O₂ remains challenging. To address this, we develop a hydrothermal pretreatment-assisted heterogeneous molten salt strategy to synthesize crystalline carbon nitride (S/Cl-CN). This approach synergistically integrates molten KSCN (enabling rapid mass transfer and in situ generation of electron-withdrawing CN groups) with solid KCl (providing spatial confinement for oriented crystallization). The heterogeneous environment optimally tunes interfacial effects, enhancing structural order and charge separation efficiency. The resulting S/Cl-CN exhibits extended visible-light absorption (narrowed bandgap 2.67 eV), accelerated carrier mobility and optimized O₂ adsorption sites via CN-induced electron redistribution. These properties enable record H₂O₂ production rates of 4.58 mM g^-1 h^-1 in pure water (17-fold higher than the reference) and 177.1 mM g^-1 h^-1 with the sacrificial agent. Mechanistic studies confirm interfacial engineering promotes two-step single-electron oxygen reduction (via stabilized OOH^⁎ and HOOH^⁎ intermediates), complementary water oxidation pathways and reduced energy barriers for O₂ activation and conversion. This work resolves electron-manipulation challenges in photocatalytic H₂O₂ synthesis and establishes a scalable molten salt platform for interface-optimized catalyst design.

Aqueous sodium-ion batteries (ASIBs) have emerged as one of the most promising candidates for large-scale energy storage devices, owing to their inherent non-flammability, abundant resources and low cost. However, the water-induced hydrogen evolution reaction (HER) on the anode surface usually leads to low Coulombic efficiency (CE) and limited cycling stability. In this study, we propose a novel aqueous electrolyte recipe composed of H₂O/DMF/TTE-NaTFSI to mitigate the issue of HER. On the one hand, the 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TTE), acting as a diluent, is highly hydrophobic. It disrupts the hydrogen-bonding network of H₂O, thereby enhancing solvation kinetics. Furthermore, the fluorinated moieties of TTE interact with H₂O molecules via strong dipole interactions, reducing solvent mobility and optimizing the Na⁺ solvation sheath. On the other hand, the N, N-dimethylformamide (DMF) serves as a co-solvent that promotes miscibility between aqueous phase and TTE while restructuring the hydrogen-bonding network within the solvation shell. DMF and TTE regulate synergistically the primary solvation structure, stabilizing Na⁺ ions via strengthened anion coordination and effectively suppressing HER. Consequently, the ASIB demonstrates exceptional cyclic stability, retaining 99.2% of its capacity after 1000 cycles at 1C and 96.3% after 100 cycles at 2C in Na₃V₂(PO₄)₃/C full cells. This work presents a promising strategy to suppress HER through the synergistic interaction between DMF and TTE, enhancing electrochemical performance.

Ruthenium-based materials are recognized as theoretically ideal bifunctional catalysts for acidic overall water splitting. However, their practical implementation remains constrained by critical challenges, such as the dissolution and over-oxidation of active sites under operating conditions. In this study, through precise modulation of the electronic structure at the Ru-RuO₂ heterojunction interface without incorporating any foreign metal elements, we successfully constructed a unique configuration characterized by compressed RuO bonds. Combined experimental characterization and theoretical calculations reveal that interfacial electron transfer induces the compression of RuO bond lengths, which subsequently leads to a downshift of the d-band center compared to pure RuO₂. This electronic modulation effectively optimizes the adsorption behavior of both oxygen and hydrogen intermediates, thereby simultaneously lowering the energy barriers for the oxygen evolution reaction and the hydrogen evolution reaction. The synthesized Ru-RuO₂@NC catalyst shows impressive bifunctional performance in an acidic electrolyte environment, reaching overpotentials as low as 161 mV for the oxygen evolution reaction and 53 mV for the hydrogen evolution reaction at a current density of 10 mA cm^-2. Additionally, it demonstrates outstanding durability, sustaining stable performance for more than 420 h at 10 mA cm^-2 during oxygen evolution reaction (OER) and 160 h even at a high current density of 500 mA cm^-2 for the hydrogen evolution reaction (HER). This research offers fresh theoretical perspectives and a methodological framework aimed at realizing efficient and stable acidic overall water splitting by means of interface bond manipulation.

Coordination metallopolymers (CMPs) have emerged as promising candidates for integrated electrochromic energy storage applications, leveraging their tunable structures that allow for precise control over their optical, electronic, and mechanical properties. However, achieving synergistic enhancement in both electrochromic and energy storage performance remains a significant challenge. To address this, we designed and synthesized two novel D-π-D structured CMPs featuring multiple redox-active centers by virtue of a π-conjugation engineering strategy via facile liquid-liquid interfacial polymerization. The resultant device achieved a high optical contrast of 54.1% at 750 nm, an improved area specific capacitance of 30.46 mF·cm^-2, and a rapid switching speed (2.3 s/1.2 s), attributed to efficient intramolecular charge delocalization and rapid charge transfer kinetics, stemming from the D-π-D molecular architecture. The fabricated smart window demonstrates an effective thermal insulation performance of 14.4 °C temperature reduction versus a general glass window. Furthermore, the electric energy involved in electrochromism could be recycled to power an LED for 30 s. This work provides a viable design strategy for developing high-performance CMPs with integrated electrochromic and energy storage functions.

Hydrated V₂O₅ is a promising cathode material for aqueous zinc-ion batteries (ZIBs), where interlayer structural H₂O plays a crucial role in tuning Zn²⁺ storage performance. Nevertheless, the precise modulation of interlayer H₂O content remains a major challenge in material synthesis. Herein, we employ pre-intercalated K⁺ ions as structural mediators to modulate the interlayer H₂O content in hydrated V₂O₅, successfully synthesizing K_0.4V₂O₅·0.24H₂O (KVOH) with an optimized hydrated structure. The engineered hydration structure creates a greatly favorable interlayer electrostatic shielding microenvironment that effectively weakens the attraction between intercalated Zn²⁺ and VO framework, thereby facilitating highly reversible and rapid Zn²⁺ (de)intercalation. Simultaneously, the pre-intercalated K⁺ ions and interlayer H₂O molecules act as structural pillars that cooperatively stabilize the host framework during prolonged charge/discharge cycling. Benefiting from these advantages, KVOH delivers a high zinc storage capacity of 469.6 mAh g^-1 at 0.5 A g^-1 and maintains 88.2% of its initial capacity after 500 cycles. Moreover, it also demonstrates outstanding long-term cycling stability, achieving 79.0% capacity retention after 5000 cycles at 10 A g^-1. This work reveals the crucial role of interlayer hydration chemistry in governing Zn²⁺ storage performance and provides a novel strategy for precisely modulating interlayer water content in hydrated V₂O₅ cathodes.

Achieving precise "on-off" control over hydrogen release is crucial for the efficient on-demand utilization of hydrogen energy. This study proposes a novel solid-state storage strategy, which involves loading ammonia borane (AB) and a cobalt catalyst into a graphene aerogel (AB@Co/RGOA), to regulate hydrogen generation via water-mediated hydrolysis. Characterization reveals that Co nanoparticles are uniformly dispersed on the graphene aerogel, while AB is effectively encapsulated within the structure to form a bulk solid composite. This AB@Co/RGOA system enables switchable hydrogen production, which can be precisely initiated and halted by modulating the water supply to the aerogel. Furthermore, the Co-decorated RGO framework (Co/RGOA) remains intact after AB is fully consumed and can be reloaded with fresh AB for subsequent cycles. The catalyst exhibits favorable catalytic activity toward AB hydrolysis with a turnover frequency (TOF) of 109.63 min^-1 at 25 °C. Moreover, the catalyst retains over 90% of its initial activity after five cycles of reuse. This work not only presents a viable approach to managing hydrogen release for potential on-board applications but also establishes a generalizable strategy that can be adapted to other catalyst-loaded porous materials for controlled hydrolytic hydrogen generation.

Heterojunction construction has been widely regarded as a pivotal strategy for enhancing photocatalytic CO₂ conversion of Ni-MOF and employing the post-synthetic modification (PSM) strategy can further improve the electron transport efficiency and increase the reaction active sites of MOF-based materials. Hence, in this study, a novel SiC/Ni-MOF derivatives dual heterojunction (Ni/C/SiC/Ni-MOF) with Schottky and Type-II was designed and synthesized via an in-situ hydrothermal followed by pyrolysis in N₂ atmosphere. The metallic Ni nanoparticles formed during pyrolysis acted simultaneously as active sites and electron accumulation hubs. Furthermore, the strong interfacial interactions of SiC/Ni-MOF type-II heterojunction and Schottky barrier between Ni and SiC facilitated efficient charge transfer across the interfaces. The coexistence of defective C and graphitic C optimized the adsorption of CO₂ and electron transport. In-situ DRFTIR analysis confirmed the formation of key intermediates *COOH and *CHO, which are vital for CO₂ conversion to CO and CH₄. Density functional theory (DFT) calculations revealed the electron transfer route with the existence of internal electron field (IEF). Meanwhile, the energy level matching among graphitic C, SiC and Ni resulted in the accumulation of electrons on metallic Ni. Under simulated sunlight irradiation, the evolution rates of CO and CH₄ on SiC/Ni-MOF pyrolyzed at 400 °C (S/N-400) achieved 7.42 μmol·g^-1·h^-1 and 16.75 μmol·g^-1·h^-1, respectively with a CH₄ selectivity as high as 90.0%. This work provides a feasible strategy for constructing dual heterojunction with synergistic effects to accomplish efficient CO₂ conversion.