Strong Electrostatic Interactions Research Articles

Molecular Weaving Towards Flexible Covalent Organic Framework Membranes for Efficient Gas Separations.

Covalent organic frameworks (COFs) exhibit considerable potential in gas separations owing to their remarkable stability and tunable pore structures. Nevertheless, their application as gas separation membranes is hindered by limited size-sieving capabilities and poor processability. In this study, we propose a novel molecular weaving strategy that combines hydroxyl polymers and 2D TpPa-SO3H COF nanosheets, achieving high gas separation efficiency. Driven by the strong electrostatic interactions, the hydroxyl chains thread through the COF pores, effectively weaving and assembling the composites to achieve exceptional flexibility and high mechanical strength. The penetrated chains also reduce the effective pore size of COFs, and combined with the "secondary confinement effect" stemming from abundant CO2 sorption sites in the channels, the PVA@TpPa-SO3H membrane demonstrates a remarkable H2 permeance of 1267.3 GPU and an H2/CO2 selectivity of 43, surpassing the 2008 Robson upper bound limit. This facile strategy holds promise for the manufacture of large-area COF-based membranes for small-sized gas separations.

Molecular Weaving Towards Flexible Covalent Organic Framework Membranes for Efficient Gas Separations

AbstractCovalent organic frameworks (COFs) exhibit considerable potential in gas separations owing to their remarkable stability and tunable pore structures. Nevertheless, their application as gas separation membranes is hindered by limited size‐sieving capabilities and poor processability. In this study, we propose a novel molecular weaving strategy that combines hydroxyl polymers and 2D TpPa−SO3H COF nanosheets, achieving high gas separation efficiency. Driven by the strong electrostatic interactions, the hydroxyl chains thread through the COF pores, effectively weaving and assembling the composites to achieve exceptional flexibility and high mechanical strength. The penetrated chains also reduce the effective pore size of COFs, and combined with the “secondary confinement effect” stemming from abundant CO2 sorption sites in the channels, the PVA@TpPa−SO3H membrane demonstrates a remarkable H2 permeance of 1267.3 GPU and an H2/CO2 selectivity of 43, surpassing the 2008 Robson upper bound limit. This facile strategy holds promise for the manufacture of large‐area COF‐based membranes for small‐sized gas separations.

Architecting V2O5 with a Triune Crystal Water-Amorphous-Crystalline Feature for Robust Zinc-Ion Batteries.

The notorious collapse of the electrode structure and strong electrostatic interactions in aqueous zinc-ion batteries (AZIBs) limit the achievement of a long cycle life. Herein, by designing an ordered/disordered hybrid structure, we have effectively preserved the integrity of the V2O5·1.6H2O (VOH) electrode. Moreover, our approach facilitates the release of stress concentration contributed to by the amorphous component, alleviating the strong electrostatic interaction merited by crystal water and promoting the diffusion kinetics of Zn2+ assisted by the crystalline component. Noteworthy, the crystal water serves as an interlayer pillar significantly enhancing the structural stability of the electrode. As a result, our VOH electrode exhibits high electrochemical performance. It delivered 227.8 mAh g-1 at a higher current density of 2 A g-1, and a high cycle life of 1000 cycles with 95% capacity retention was achieved at a current density of 1 A g-1.

Construction and Evaluation of pH‐Responsive Nitrogen‐Containing Metal–Organic Frameworks as Oral Drug Carriers

ABSTRACTMetal–organic framework (MOF) is a porous material composed of metal ions/clusters and organic ligands. It has attracted much attention due to its high specific surface area, good biocompatibility, chemical modifiability, and diversity of components. Among many MOFs, zirconium‐based MOFs are particularly suitable for biological applications due to their optimal stability and low toxicity to hydrolysis. However, due to the weak coordination bonds between many metal clusters and organic ligands, most MOFs are prone to collapse in acidic environments, and the stability of MOFs as drug carriers cannot be guaranteed so that they cannot be widely used as oral drug carriers. This study synthesized the three MOFs using metal Zr ion clusters as the center and different nitrogen‐containing organic ligands, which are stable in gastric acid, namely, UiO‐66‐PDC, UiO‐66‐NH2, and UiO‐66‐NO2. The anionic drug loxoprofen (LOX) was loaded and characterized using scanning electron microscopy, infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and x‐ray diffraction. The adsorption and release behaviors of LOX and the three MOFs were studied from the molecular point of view by computer simulation. A series of behaviors and mechanisms of pH‐responsive nitrogen‐containing MOFs as oral drug carriers were further explored through rat pharmacokinetic experiments, the everted gut sac experiments, and intestinal absorption mechanism experiments. The experimental results show that there is a strong electrostatic interaction between anionic drug LOX and UiO‐66‐PDC under simulated gastric acid environment, which prolongs the half‐life of the drug, proving that LOX@UiO‐66‐PDC is a promising new oral drug delivery system.

Electrostatically Dominated Pre-Organization inCyclodextrin Metal-Organic Frameworks.

Electrostatic interactions between oppositely charged entities play a key role in pre-organizing substrates and stabilizing transition states of reactions in enzymes. The use of electrostatic interactions to pre-organize ions in nanoconfined pores, however, has not been investigated to its full potential. Herein, we describe how carboxylate anions can be pre-organized at the behest of their electrostatic interactions with K+ cations in nanoconfined tunnels present in γ-cyclodextrin metal-organic frameworks, i.e., CD-MOFs. Several carboxylate anions, which are all much smaller than the cavities of the tunnels, were visualized by X-ray crystallography when nanoconfined in CD-MOFs, despite the large voids present in the tunnels. These anions were found to be aligned within a planar array defined by four K+ cations, positioned around the periphery of the tunnels. The strong electrostatic interactions between the carboxylate anions and the K+ cations dictate the orientation of the anions and override the influence of other possible noncovalent bonding interactions between them and the tunnels. Consequently, the aligned pairs of γ-cyclodextrin rings constituting the tunnels become distorted, resulting in their lower symmetry and fewer disordered carboxylate anions in the solid-state. Our findings offer a transformative strategy for controlling the packing and orientation of ions in nanoconfined environments.

Elucidating the Supramolecular Interaction of Positively Supercharged Fluorescent Protein with Anionic Phthalocyanines.

Developing bioinspired materials to convert sunlight into electricity efficiently is paramount for sustainable energy production. Fluorescent proteins are promising candidates as photoactive materials due to their high fluorescence quantum yield and absorption extinction coefficients in aqueous media. However, developing artificial bioinspired photosynthetic systems requires a detailed understanding of molecular interactions and energy transfer mechanisms in the required operating conditions. Here, the supramolecular self-assembly and photophysical properties of fluorescent proteins complexed with organic dyes are investigated in aqueous media. Supercharged mGreenLantern protein, mutated to have a charge of +22, is complexed together with anionic zinc phthalocyanines having 4 or 16 carboxylate groups. The structural characterization reveals a strong electrostatic interaction between the moieties, accompanied by partial conformational distortion of the protein structure, yet without compromising the mGreenLantern chromophore integrity as suggested by the lack of emission features related to the neutral form of the chromophore. The self-assembled biohybrid shows a total quenching of protein fluorescence, in favor of an energy transfer process from the protein to the phthalocyanine, as demonstrated by fluorescence lifetime and ultrafast transient absorption measurements. These results provide insight into the rich photophysics of fluorescent protein-dye complexes, anticipating their applicability as water-based photoactive materials.

Stabilization of the Compressed Planar Benzene Dianion in Inverse-Sandwich Rare Earth Metal Complexes.

For the first time, the capture of a planar antiaromatic benzene dianion in between two trivalent rare earth (RE) metal cations, each stabilized by two guanidinate ligands, is reported. The synthesized inverse-sandwich complexes [{(Me3Si)2NC(NiPr)2}2RE]2(µ-ƞ6:ƞ6-C6H6), (RE = Y (1), Dy (2), and Er (3)) feature a remarkably planar benzene dianion, previously not encountered for any metal ion prone to low or absent covalency. The -2 charge localization at the benzene ligand was deduced from the results obtained by single-crystal X-ray diffraction analyses, spectroscopy, magnetometry, and Density Functional Theory (DFT) calculations. In the 1H NMR spectrum of the diamagnetic Y complex 1, the equivalent proton resonance of the bridging benzene dianion ligand is drastically shifted to higher field in comparison to free benzene. This and the calculated highly positive Nucleus-Independent Chemical Shift (NICS) values are attributed to the antiaromatic character of the benzene dianion ligand. The crucial role of the ancillary guanidinate ligand scaffold in stabilizing the planar benzene dianion conformation was also elucidated by DFT calculations. Remarkably, the planarity of the benzene dianion originates from the stabilization of the π-type orbitals of the d-manifold and compression through its strong electrostatic interaction with the two REIII sites.

Stabilization of the Compressed Planar Benzene Dianion in Inverse‐Sandwich Rare Earth Metal Complexes

For the first time, the capture of a planar antiaromatic benzene dianion in between two trivalent rare earth (RE) metal cations, each stabilized by two guanidinate ligands, is reported. The synthesized inverse‐sandwich complexes [{(Me3Si)2NC(NiPr)2}2RE]2(µ–ƞ6:ƞ6–C6H6), (RE = Y (1), Dy (2), and Er (3)) feature a remarkably planar benzene dianion, previously not encountered for any metal ion prone to low or absent covalency. The ‐2 charge localization at the benzene ligand was deduced from the results obtained by single‐crystal X‐ray diffraction analyses, spectroscopy, magnetometry, and Density Functional Theory (DFT) calculations. In the 1H NMR spectrum of the diamagnetic Y complex 1, the equivalent proton resonance of the bridging benzene dianion ligand is drastically shifted to higher field in comparison to free benzene. This and the calculated highly positive Nucleus‐Independent Chemical Shift (NICS) values are attributed to the antiaromatic character of the benzene dianion ligand. The crucial role of the ancillary guanidinate ligand scaffold in stabilizing the planar benzene dianion conformation was also elucidated by DFT calculations. Remarkably, the planarity of the benzene dianion originates from the stabilization of the π‐type orbitals of the d‐manifold and compression through its strong electrostatic interaction with the two REIII sites.

Effect of conditioners used for sludge dewatering on the adsorption performance of sludge-derived adsorbent

Converting waste activated sludge into adsorbent is a promising alternative for sludge valorization. While various conditioners are widely employed in sludge conditioning and dewatering processes, the influence of these conditioners on the properties of sludge derived adsorbents remains largely unexplored. Four conditioners, including FeCl3, CaO, polyacrylamide, FeSO4·7 H2O/Na2S2O8, were used for sludge conditioning, and the sludge dewaterability and the adsorption performance of the resultant adsorbents were evaluated. The sludge dewaterability was markedly improved by the conditioners in a descending order as polyacrylamide, FeCl3, FeSO4·7 H2O/Na2S2O8, and CaO. The type of conditioner highly influenced the adsorption ability of the sludge adsorbent: FeSO4·7 H2O/Na2S2O8 enhanced the adsorption ability, while others deteriorated it. Infrared spectra, pore size distribution, and micromorphology analysis of the adsorbents suggest that: FeCl3 reduced mesopores through strong electrostatic interactions; CaO acted as a physical barrier for adsorption; polyacrylamide reduced the adsorbent surface area through hydrogen bond-driven bridging and potentially forming polymeric barrier; FeSO4·7 H2O/Na2S2O8 disrupted the sludge flocs and exposed abundant adsorption sites, promoting the adsorbent performance markedly. FeSO4·7 H2O/Na2S2O8 conditioning was thus beneficial to both sludge dewatering and adsorption. Adsorption of methylene blue by FeSO4·7 H2O/Na2S2O8-conditioned sludge adsorbent was best described by the pseudo-second-order model and Langmuir model, indicating the dominance of monolayer chemisorption. The adsorption mainly occurred in the mesopores of the adsorbent, with hydroxyl group and carbonyl in carboxyl group as the main binding sites. Both film and pore diffusion contributed to the adsorption rate, with pore diffusion serving as the main rate limiting step. Results highlight the beneficial effect of destructive conditioning method on sludge adsorbent performance.

Chemokine Receptor N-Terminus Charge Dictates Reliance on Post-Translational Modifications for Effective Ligand Capture and Following Boosting by Defense Peptides.

The chemokine receptors CCR1 and CCR5 display overlapping expression patterns and ligand dependency. Here we find that ligand activation of CCR5, not CCR1, is dependent on N-terminal receptor O-glycosylation. Release from O-glycosylation dependency is obtained by increasing CCR5 N-terminus acidity to the level of CCR1. Ligand activation of CCR5, not CCR1, drastically improves in the absence of glycosaminoglycans (GAGs). Ligand activity at both CCR1 and CCR5 is boosted by positively charged/basic peptides shown to interact with acidic chemokine receptor N-termini. We propose that receptors with an inherent low N-terminus acidity rely on post-translational modifications (PTMs) to efficiently compete with acidic entities in the local environment for ligand capture. Although crucial for initial ligand binding, strong electrostatic interactions between the ligand and the receptor N-terminus may counteract following insertion of the ligand into the receptor binding pocket and activation, a process that seems to be aided in the presence of basic peptides. Basic peptides bind to the naked CCR1 N-terminus, not the CCR5 N-terminus, explaining the loss of boosting of ligand-induced signaling via CCR5 in cells incapable of glycosylation.

Strong, tough self-healing multi-functional sodium alginate-based edible composite coating for banana preservation

Edible coatings are a new green technology for preventing the rotting of fruits and extending their shelf lives. However, during storage, respiratory processes can generate large amounts of water, causing the dissolution of these coating. Furthermore, these coating can be mechanically damaged. Therefore, the development of strong, tough, waterproof and self-healing edible coatings is highly desirable. Herein, gluconolactone was slowly oxidized to generate gluconic acid, which was further used to protonate amino groups in wheat gluten (WG), forming strong electrostatic interactions, hydrogen bonds and ester bonds between soy hull nanocellulose (SHNC) and sodium alginate (SA). The introduction of WG and SHNC improved the mechanical strength, hydrophobicity and water retention of the composite film from 28 MPa, 33.2° ± 1.18° and 19.43° ± 0.83° to 60 MPa, 45.13° ± 1.53° and 41.47° ± 0.96°, respectively. Further, the composite film exhibited excellent self-healing, UV resistance and gas-barrier properties. Banana preservation experiments showed that at 25 °C and 50 % RH, the composite coating effectively slowed the mass loss and softening of bananas, delayed the browning of banana peels and ripening of fruit pulp, and extended the shelf life of bananas to 7 days. Therefore, this study provides a new perspective for the preparation of a new, strong, tough, waterproof and self-healing multi-functional edible coating with high potential for the preservation of perishable fruits.

Zwitterion Intercalated Manganese Dioxide Nanosheets as High-Performance Cathode Materials for Aqueous Zinc Ion Batteries.

In this study, a novel approach is introduced to address the challenges associated with structural instability and sluggish reaction kinetics of δ-MnO2 in aqueous zinc ion batteries. By leveraging zwitterionic betaine (Bet) for intercalation, a departure from traditional cation intercalation methods, Bet-intercalated MnO2 (MnO2-Bet) is synthesized. The positively charged quaternary ammonium groups in Bet form strong electrostatic interactions with the negatively charged oxygen atoms in the δ-MnO2 layers, enhancing structural stability and preventing layer collapse. Concurrently, the negatively charged carboxylate groups in Bet facilitate the rapid diffusion of H+/Zn2+ ions through their interactions, thus improving reaction kinetics. The resulting MnO2-Bet cathode demonstrates high specific capacity, excellent rate capability, fast reaction kinetics, and extended cycle life. This dual-function intercalation strategy significantly optimizes the electrochemical performance of δ-MnO2, establishing it as a promising cathode material for advanced aqueous zinc ion batteries.

Synthesis and optimization of chitosan-incorporated semisynthetic polymer/α-Fe2O3 nanoparticle hybrid polymer to explore optimal efficacy of fluorescence resonance energy transfer/charge transfer for Co(II) and Ni(II) sensing

Initially, four synthetic fluorescent polymers (SFPs) are synthesized from α-methacrylic acid and methanolacrylamide monomers carrying –C(=O)OH and –C(=O)NH subfluorophores, respectively. Among SFPs, ∼1:1 incorporation of subfluorophores in the optimum SFP3 is explored by spectroscopic analyses. Subsequently, chitosan is incorporated in SFP3 to produce five semi-synthetic fluorescent polymers (SSFPs). The maximum incorporation of chitosan in SSFP4 is supported by different spectroscopies. In SSFP4, strong electrostatic interactions among polar functionalities of chitosan and synthetic polymer favor resonance-associated charge transfer (RCT) from SSFP4-(amide) to SSFP4-(canonical). Finally, three hybrid fluorescent polymers (HFPs) are fabricated encapsulating iron-oxide nanoparticle within SSFP4. The maximum proportion of hematite (α-Fe2O3) phase in HFPs is explored by spectroscopic, magnetometric, microscopic, and light scattering studies. HFP2 shows local/RCT/fluorescence resonance energy transfer (FRET) emission at 393/460/570 nm. In HFP2, FRET, RCT, and ratiometric pH-sensing within 3.0–6.5 phenomena are explored by solvent polarity effects, time-correlated single photon counting, quantum yield measurements, alongside I431/I460 vs pH plots. RCT and FRET emissions of HFP2 are utilized for selective sensing of Co(II)/Ni(II) with limits of detection of 4.990 ppb (460 nm)/4.353 ppb (570 nm) and 45.041 ppb (428 nm)/29.617 ppb (527 nm) in organic and aqueous solutions, respectively.

Mechanism of the G/M ratio and zein in enhancing the mechanical and hydrophobic properties of sodium alginate films

This study developed an edible film based on calcium-crosslinked sodium alginate (SA) using the casting method. The investigation assessed how the α-L-guluronic acid/β-D-mannuronic acid (G/M ratio) and zein addition influence the film's physicochemical properties. Fourier transform infrared spectroscopy and scanning electron microscopy findings suggest that the G/M ratio modulates the film's physicochemical characteristics by altering SA molecular cross-linking strength and the film's network structure density. At a G/M ratio of 0.85, the film exhibits a more uniform network structure, enhanced moisture resistance, hydrophobicity, and mechanical properties. Zein, evenly dispersed within the film matrix, establishes strong hydrogen bonds and electrostatic interactions with SA, enhancing the film's network structure and boosting its thermophysical, mechanical, and moisture resistance characteristics. The study demonstrates that modifying the G/M ratio and incorporating zein enhances the film's mechanical and hydrophobic properties, broadening its potential applications in food packaging.

Self-Polymerized Tough and High-Entanglement Zwitterionic Functional Hydrogels.

Zwitterionic hydrogels exhibit great potential in biomedical applications due to their antifouling properties and biocompatibility. However, the single-network structure of pure zwitterionic hydrogels leads to a low toughness and strength, limiting their application in biomedical fields. In this work, a high entanglement sulfobetaine methacrylate-dopamine hydrogel (SBMA-DA-PE) with low cross-linker content and high monomer concentration is prepared by using a dopamine oxidative radical polymerization method. Compared to a regular zwitterionic hydrogel, the SBMA-DA-PE hydrogel exhibits a 5-fold increase in tensile fracture stress and a 10-fold increase in compressive fracture stress. The SBMA-DA-PE hydrogel possesses excellent mechanical properties (the maximum compressive stress ≥4.85MPa, the maximum compressive strain ≥90%). Besides, the non-covalent interactions between catechol or ortho-quinones within the SBMA-DA-PE hydrogel, combined with strong intermolecular electrostatic interactions, endow the SBMA-DA-PE hydrogel with great self-healing capabilities and fatigue resistance. The SBMA-DA-PE hydrogel demonstrates low swellability and possesses good antifouling properties. Furthermore, the good printability and conductivity of the tough SBMA-DA-PE hydrogel endows it with new possibilities for developing biological 3D scaffolds and electronic devices. Overall, this work provides new insights into the preparation of zwitterionic hydrogels with high mechanical strength and multi-functionality for biomedical applications.

Characterization of NK-lysin A, a potent antimicrobial peptide from the zebrafish Danio rerio

Antimicrobial peptides (AMPs) are important players of the innate immune system with a major role in the defense against invading pathogens. AMPs belonging to the family of saposin-like proteins (SAPLIPs) include the porcine NK-lysin and the human granulysin. In the zebrafish Danio rerio, transcript analyses of NK-lysin encoding genes have been reported, but biochemical characterizations at the protein level are missing so far. Here, we present the recombinant expression, purification, and characterization of one of these homologs, namely of NK-lysin A (DaNKlA). To remove the affinity tag from DaNKlA, we made use of a self-splicing intein. Recombinant DaNKlA depolarized liposomes over a broad pH range and showed a preference for negatively charged lipids. DaNKlA inhibited the growth of and killed different Gram-positive and Gram-negative bacteria, including the fish pathogenic bacterium Vibrio anguillarum, by membrane permeabilization but displayed substantially lower activity against yeast cells. Structural modelling and bioinformatic comparison of DaNKlA with characterized SAPLIPs suggest membrane destabilization accompanied by strong electrostatic interactions as the mode of action.

Supramolecular assembly strategy of modified starch chains for achieving recyclable emulsion biocatalysis within a narrow pH range

Stimuli-responsive Pickering emulsions are promising in biocatalysis for their ease of product separation and emulsifier recovery. However, pH responsiveness, though simple and cost-effective, faces challenges in precise control and narrow transition ranges, limiting its use in enzymatic catalysis. Herein we introduced amorphous octenyl succinic anhydride-modified debranched starch chains (Am-OSA-St) to control emulsion properties within a pH range suitable for enzymatic catalysis. By adjusting the OSA group density and molecular weight, Am-OSA-St allowed emulsions to transition reversibly between pH 7.3 and 5.5 and enabled self-recycling through supramolecular self-assembly. Employing molecular dynamics simulations and physicochemical characterization, we elucidated the control mechanism of oil-water interfaces via the microstructure transformation of Am-OSA-St. The findings revealed that protonation of carboxylate groups disrupted the charge balance and polarity of starch chains, leading to strong electrostatic and van der Waals interactions that drove self-assembly. This entanglement caused starch chains in the aqueous phase to “drag” those at the oil-water interface, moving them into the aqueous phase and forming micelles. These micelles, with a hydrophobic interior and hydrophilic exterior, prevented re-adsorption. Testing with Candida antarctica Lipase B (CALB) and N-acetylneuraminic lyase showed that the pH-regulated emulsion system maintained excellent efficiency and cycling stability in mild conditions.

Effects of 2-ethylbutyric acid, 2-ethyl-1-butanol, and 3-methylpentane on the micellization thermodynamics and physicochemical properties of HS 15 and TW 80 micelles based on differences in functional groups

Herein, we investigated the effects of 2-ethylbutyric acid, 2-ethyl-1-butanol, and 3-methylpentane, each possessing varying functional groups, on polyoxyl 15 hydroxystearate (HS 15) and polysorbate 80 (TW 80) micelles. Initially, the critical micelle concentration (CMC) for both systems was determined. Subsequent measurements included the particle size, zeta potential, cloud point, micropolarity, number of aggregates, and fluorophore release profile. Finally, the number of hydrogen bonds was confirmed through molecular docking technology. Results showed distinct effects of different functional groups on TW 80 and HS 15 micelles, exhibiting a decreasing trend of CMC, Amin, Gmin, particle size, and polydispersity index (PDI) with increased functional group polarity, alongside increased zeta potential, decreased cloud point, enlarged hydrophobic region, and rapid fluorophore quenching. In particular, acids with carboxyl groups exhibited enhanced stability with HS 15 and TW 80 micelles owing to differences in polarity, solubilization sites, and intermolecular forces. Using tanshinone extract as a model drug, the study explored HS 15 and TW 80 micelles as drug carriers, and results indicated that 2-ethylbutyric acid micelles exhibited better bacterial inhibition against Staphylococcus aureus. Considering that the surface of bacteria was negatively charged, the positively charged nanoparticles exhibited strong electrostatic interactions with the bacteria, which exerted a superior antibacterial effect. In summary, 2-ethylbutyric acid micelles displayed the smallest CMC, Amin, Gmin, particle size, and PDI, along with a positive charge, highlighting the potential application of 2-ethylbutyric acid.

Constructing type II heterojunction of 2D/1D Pg-C3N4/Ag3VO4 nanocomposite with high interfacial charge separation for boosting photocatalytic CO2 reduction under solar energy

The well-designed, template-free synthesis of 2D protonated g-C3N4 nanosheets (Pg-C3N4) coupled with novel 1D Ag3VO4 nanorods has been investigated to construct 2D/1D interface heterostructures with strong electrostatic interactions between the positively charged 2D Pg-C3N4 nanosheets and the negatively charged 1D Ag3VO4 nanorods. The coupling of Pg-C3N4 and Ag3VO4 with desirable characteristics resulted in a 2D/1D interface heterojunction with a type II charge carrier transfer mechanism, effectively maintaining and utilizing charge carriers. The 2D/1D Pg-C3N4/Ag3VO4 exhibited remarkable photocatalytic performance for CO2 conversion with H2O, resulting in maximum CH4 and dimethyl ether (DME) production of 352.3 and 130.9 µmol/g-cat, respectively. A quantum yield of 0.23 % for CH4 generation was achieved over the 2D/1D Pg-C3N4/Ag3VO4, which was 2.9 and 1.4 times higher than that of the Pg-C3N4 and Ag3VO4 samples, respectively. The improvement in photocatalytic performance primarily stems from the effective interaction between Pg-C3N4 and ternary Ag3VO4, leading to enhanced transfer and separation of photoinduced charge carriers through the creation of a type II heterojunction. The findings of this study are useful in designing template-free heterojunctions for photocatalytic CO2 conversion and other solar energy applications.

Oxygen-deficient NH4V4O10 cathode with Ag quantum dots and interlayer Ag+ towards high-performance aqueous zinc ion batteries

Herein, oxygen-deficient NH4V4O10 micro-flowers with loaded Ag quantum dots and pre-intercalated Ag+ (NVO-Ag) for aqueous zinc ion battery (AZIB) cathode materials were successfully synthesized by a one-step hydrothermal method. The reversible redox reaction between Ag+ and Ag quantum dots, and the abundant Zn2+ storage sites from oxygen vacancies provided capacity contributions for NVO-Ag. Meanwhile, the loaded Ag quantum dots, pre-intercalated Ag+ and introduced oxygen vacancies synergistically optimized the electronic structure and distribution of NVO-Ag, promoting the transport of electrons in NVO-Ag. The pre-intercalated Ag+ could also replace the NH4+ in the interlayer of NH4V4O10, weakening the repulsion between the interlayer NH4+ and Zn2+, which achieved rapid Zn2+ diffusion kinetics. Moreover, the abundant oxygen vacancies in NVO-Ag could alleviate the strong electrostatic interaction between Zn2+ and V-O framework, boosting the transmission of Zn2+ in NVO-Ag. Finally, the structural stability of NH4V4O10 micro-flowers was improved due to the high bonding strength between Ag+ and V-O layers. Benefiting from the above effects, NVO-Ag-100 achieved excellent capacity performance (387.2 mAh g−1 at 0.5 A g−1), rate performance (178.9 mAh g−1 at 12 A g−1) and cycle stability (91.7 % capacity retention after 1700 cycles at 8 A g−1). This work provided effective ideas to achieve high-performance AZIB cathode materials.