JOURNAL OF COLLOID AND INTERFACE SCIENCE

Delafossite-embedded Z-scheme heterojunction photocathode with abundant heterointerfaces for boosted photoelectrochemical performance
Fu WR, Yu SM, Xiang X, Yang J and Zhao ZY
Layered delafossite, an inherently p-type semiconductor, has emerged as a highly promising photocathode material for photoelectrochemical (PEC) water splitting. However, its PEC performance and scalability are significantly limited by the shortcomings of conventional photoelectrode fabrication techniques, which often involve inferior physical adhesion or require harsh processing conditions. In this study, a CuO layer is introduced via in-situ oxidation of a copper foam (CF) substrate to achieve embedded anchoring of delafossite CuFeO (CFO), thereby developing a robust embedded CF/(CFO@CuO) photocathode. This configuration features extensive and strong 3D semiconductor/semiconductor heterointerfaces. The embedded structure significantly reduces the carrier diffusion length to the CF, thereby enhancing photocarrier collection efficiency. Additionally, this unique geometric design provides abundant heterointerfaces with all-round contact, promoting efficient carrier separation while strengthening interfacial binding. Theoretical calculations further reveal the formation of a strong built-in electric field and a Z-scheme heterostructure, which facilitate effective photocarrier separation and transfer while maintaining robust redox activity. Remarkably, the photocurrent density of the embedded CF/(CFO@CuO) photocathode at zero bias is 2.73-fold higher than that of the traditional sandwich-stacked CF/CuO/CFO photocathode and 21.55-fold higher than that of the original CF/CFO photocathode. Furthermore, the scalability of this approach is demonstrated through the fabrication of a 100 cm embedded photocathode. This work presents a scalable and cost-effective nanofabrication technique for robust photoactive films, enabling efficient and stable PEC water splitting.
Porous TiPO/nitrogen-doped carbon composite with tailored crystal orientation as diffusion-controlled high-rate anode for lithium-ion batteries
Cui W, Ma M, Sun Y, Fan Q, Zhang K and Shi C
TiPO is a lithium-ion batteries anode material with outstanding stability and high safety due to its strong polyanion three-dimensional frame structure. However, poor electrical conductivity severely represses the rate capability of TiPO anode. Herein, a porous TiPO/nitrogen-doped carbon (CN) composite with tailored (630) and (600) preferential crystallographic orientation is achieved by the ball-milling and thermal treatment strategy. The TiPO/CN (630) anode retains specific capacities of 194.3 and 128.9 mA h/g at high current densities of 5 and 10 A/g, respectively, superior than that of the TiPO/CN (600). Remarkably, kinetic analysis reveals that the charge storage process in the TiPO/CN (630) anode is predominantly diffusion-controlled, with the diffusion-controlled capacity contributing up to 52 % even at a high scan rate of 2 mV/s. Density functional theory calculation confirms the lower lithium ions migration energy barrier of (630) crystallographic orientation of TiPO. In addition, due to the homogeneity of porous structure and composition, the TiPO/CN (630) anode maintains a capacity of 389mA h/g after 1000 cycles at 1 A/g. Thereby, the synthesis strategy for preferred orientation TiPO-based anode is instructive for the structural design of high-rate metal-based composite oxides for lithium-ion batteries.
Pre-carbonization-mediated construction of urchin-like NiFeO superparticles with enhanced CNT growth for efficient oxygen evolution
Qiu J, Xi X, Zheng S, Li T, Wang Y, Ren X and Dong A
In this study, we report the rational design and synthesis of carbonized NiFeO superparticles (CarSPs) hierarchically integrated with densely aligned carbon nanotube (CNT) architectures, hereafter denoted as CarSP-CNTs, which exhibit a biomimetic urchin-like morphology. Through exploitation of the colloidal self-assembly and catalytic functionalities inherent to NiFeO nanoparticles (NPs), we achieve seamless integration of one-dimensional CNT arrays with three-dimensional superstructural frameworks. Systematic investigation reveals that the pre-carbonization of surface-bound organic ligands coupled with subsequent CNT growth induces synergistic interplay between conductive carbon matrices and active spinel oxide phases. This structural optimization confers CarSP-CNTs with enhanced charge transfer kinetics and catalytically robust interfaces, as evidenced by their superior electrocatalytic performance for the oxygen evolution reaction (OER) in alkaline electrolyte (1 M KOH). The optimized CarSP-CNTs exhibit a minimal overpotential of 307 mV to deliver a current density of 10 mA cm, alongside remarkable operational stability exceeding 20 h of continuous electrolysis. These findings establish a paradigm for the rational design of hierarchically structured, multi-component electrocatalysts through coordinated nanoscale engineering, offering a versatile platform for advancing energy conversion technologies.
Detection of isomers based on silica colloidal crystals doped with noble metals
Zhang C, Liu J and Xiong C
Structural colors (or stopbands) of different photonic crystals (PCs) could be changed by doping different concentrations of noble metals. The maximum stopband shift of PCs is about 61 nm when Pd colloid nanoparticles are doped into the PCs. Varied of PCs have been used for detecting chemicals, but it is uncommon for detection of isomers based on the simple PCs from SiO spheres and noble metals. Although difference of refractive indices of m-xylene and p-xylene is only 0.002, after noble metals as intermedium are doped into PCs, difference of the total average stopband shifts is about 37 nm. The total stopband shifts are related to diameters of SiO spheres, species of analytes, doping amounts and kinds of noble metal nanoparticles. The proposed strategy provides a convenient, cheap, trace detection method to distinguish isomers. These PCs have potential applications in display, isomer recognition and anti-counterfeiting.
Structure and phase engineering afforded gradient manganese dioxide composites for impedance matching toward electromagnetic wave absorption
Song L, Sun C, Wang Y, Huang Z, Zhao Y, Yuan S, Zhang Y and Xia W
Impedance mismatch severely limits the performance of electromagnetic (EM) microwave absorber materials. Aiming at addressing this issue, this study proposes a strategy combining structure and phase engineering to design gradient manganese dioxide (MnO) core@shell composites. The core of the composites comprises cadmium (Cd)-doped α-MnO nanowires, synthesized via a self-assembly process achieved using the hydrothermal method, which possess remarkable dielectric attenuation capability that can effectively consume EM energy. The shell comprised α-MnO nanosheets, which serve as a matching layer and introduce interfaces and defects that further enhance EM energy attenuation; notably, these α-MnO nanosheets are formed through calcination-induced phase transition of δ-MnO nanosheets grown on the core nanowire surface. The uniform growth of nanosheets on nanowires is facilitated by the low lattice mismatch between α-MnO and δ-MnO. The resulting Cd-doped α-MnO nanowire@α-MnO nanosheet composites deliver remarkable absorption performance; the minimum reflection loss can reach - 50.50 dB and effective absorption bandwidth reaches 5.44 GHz in the Ku band, which are attributed to optimized synergy between attenuation and impedance matching, dipole polarization enhancement through heteroatom doping, and interfacial polarization at the core-shell interface. This study provides a novel approach to designing advanced EM absorption materials.
Interface control in TiO/BaTiO ferroelectric heterostructures: A bidirectional catalytic pathway toward high-performance Li-S batteries
Xu X, Dou H, Zhao Z, Ali R, Zhe R, Zheng L, Bao X, Fan B and Wang HE
Li-S batteries (LSBs), noted for their high energy density and low cost, face challenges due to sluggish lithium polysulfide (LiPS) redox kinetics and complex phase transformations during charge/discharge cycles. Herein, we introduce a novel hollow nanocomposite, a titanium oxide/barium titanate (TiO/BaTiO) heterostructure with an ultrathin carbon coating, designed to act as a bidirectional electrocatalyst, enhancing the sequential conversion of sulfur (S) to LiS and then to lithium sulfide (LiS). The ferroelectric nature of BaTiO enhances LiPS adsorption, reducing the shuttling effect and improving battery performance. The interface-induced electric field directs LiPS migration to TiO, facilitating the redox process. An applied electric field polarizes the heterostructure, optimizing the dipole moment of BaTiO and further enhancing performance. Electrochemical measurements and theoretical calculations confirm the superior electrocatalytic activity of TiO/BaTiO@C for LiPS redox kinetics. The composite electrode achieves a high initial capacity of 836 mAh g at 1C, retaining 64 % of its capacity after 400 cycles with a low fading rate of 0.075 % per cycle. Under practical operation conditions (sulfur areal loading: 6.02 mg cm; electrolyte/sulfur (E/S) ratio: 6.5 μL mg), the as-fabricated LSBs still demonstrate good areal capacities of 5.18, 4.09, 3.84, 3.64, and 3.15 mAh cm, respectively, at current densities from 0.05 to 0.5C. This study elucidates the critical synergy between self-induced electric fields and heterostructure engineering in polysulfide conversion, providing fundamental guidance for designing advanced catalysts in high-energy LSBs and related electrochemical energy systems.
Construction of 2D/2D α-FeO/g-CN Z-scheme photocatalysts with SnO as an energy platform for directed charge transfer in cascade heterojunction: Photocatalytic CO reduction and pollutant degradation
Muhammad W, Faqir N, Khan MA, Khan ZU, Ahmad B, Ahmad MJ, Zada A, Ali F, Nadeem S, Ansar MZ and Ali W
Developing an efficient visible-light-driven photocatalysts for conversion of atmospheric CO into valuable fuels is a promising strategy to mitigate the escalating greenhouse gas, environmental, and energy crisis. This study presents an innovative design for a cascade Z-scheme comprising of dimensional matched SnO-α-FeO/g-CN (SO-FO/CN) nanosheets heterojunction. In this configuration, SnO functions as an optimal energy platform that not only facilitates charge transfer and separation but also sustains sufficient thermodynamic energy for redox reactions and inhibits the undesired type-II charge transfer pathway. The optimized cascade Z-scheme exhibits a remarkable 20-fold improved photoactivity for CO conversion to CH and CO compared to bare g-CN (CN). It also shows significantly improved photocatalytic activity for the degradation of toxic organic pollutants, 2,4-dichlorophenol (2,4-DCP) ∼6.6-fold and bisphenol A (BPA) ∼4.2-fold, respectively. The improved photocatalytic activity results from effective charge separation facilitated by the Z-scheme, along with a favorable energy platform and extended charge lifetime. This innovative strategy, which utilize an energy platform, presents a promising approach for designing an efficient Z-scheme heterojunction photocatalysts for solar-to-fuel conversion and pollutant degradation.
Constructing zinc defects in zinc oxide and interface-anchoring of tricobalt tetraoxide: Modulating d-band center for efficient peroxymonosulfate activation
Xie H, Gao J, Lin H, Xing J, Dai F, Wang L and Xu J
Heterojunction catalysts with defects are effective for electron transfer and peroxymonosulfate (PMS) activation. In this study, a Zn vacancy-rich ZnO/CoO (ZnO/CoO) catalyst featuring Zn-O-Co interfacial bonds was synthesized with ZnO as a matrix. Its ability to activate PMS for the degradation of ciprofloxacin (CIP) was investigated. The ZnO/CoO achieved nearly complete CIP degradation within 20  min under 17 W sterilamp irradiation. The normalization kinetic constant was 21.7 min M, which is 7.2 times higher than that of ZnO. Experimental results and theoretical calculations demonstrated that the Zn vacancy and Co species synergistically enhanced PMS adsorption. The incorporation of Co facilitated the desorption of adsorbed species from the Zn site by lowering the d-band center and promoted electron transfer to PMS. Sterilamp irradiation facilitated the generation of active radicals. The catalyst exhibited high CIP degradation ratios in the continuous-flow experiment, with over 90 % of CIP degraded within 180 min. This study presents a novel approach to enhance the catalytic activity of ZnO for pollutants degradation.
Manipulating the Li/Ni/Fe mixed configuration promotes structure stability of Li-rich layered oxides
Nan Y, Liu Z, Wu Z, Qu P, Wang Z, Tai Z, Wang H, Chen S, Chen Y, Guo S and Liu Y
Lithium-rich layered oxides (LLOs) are highly promising for applications in Li-ions batteries as the cathode materials due to their high energy density. However, LLOs often suffer from significant capacity and voltage loss due to the instability of the layered structure when in the deep extraction state. This inherent instability poses a considerable challenge to their practical application. Herein, a distinctive Li/Ni/Fe mixed configuration was constructed by using the exchange mechanism of Fe ions with Li and Ni ions in the Li layer. This configuration not only improves structural stability, but also expands the layer spacing to accelerate Li diffusion. Density functional theory (DFT) calculations indicate that the presence of Li/Ni/Fe mixed configuration leads to more Li - O - Li configurations and decreasing the characteristic energy gap above the Fermi energy level. This configuration also effectively increases the migration energy barrier of transition metal (TM) ions and oxygen (O) vacancy formation energy, which reducing the irreversible migration of TM ions and the escape of O. The target material exhibits high-capacity retention of 82.1 % after 300 cycles at 1C, accompanied by a minimal voltage fading rate of just 0.33 mV/cycle. This study offers innovative strategies to enhance the stability of LLOs, facilitating their widespread commercial use.
Engineered cell nanovesicle antagonists for androgen deprivation therapy of melanoma
Zhao Y, Ma Y, Leng Q, Zhang Q, Li Y, Ji M, Yang H, Li X, Jia G, Li Z, Liu H and Zhang J
Epidemiological studies on melanoma have revealed significant gender disparities, with the incidence and mortality rates being higher in males than in females. Recent studies indicate that androgen contributing to T cell exhaustion and promoting cancer cell proliferation. While clinical androgen deprivation therapies (ADT),particularly the use of androgen receptor (AR) antagonists to block AR signaling, has been employed in clinical settings to reduce androgen levels, antiandrogen drugs often encounter challenges such as poor targeting and selectivity, increased toxicity, low stability, short half-life and the emergence of drug resistance. Here, we establish a nanoantagonists for efficient AR signaling blockade by arming antigen-activated dendritic cells (DCs) nanovesicles with AR antibodies (aAR-NV). This innovative approach demonstrates dual therapeutic efficacy: aAR-NV effectively disrupts androgen-AR interactions in both melanoma cells and T cells, simultaneously inhibiting tumor proliferation and reversing T cell exhaustion. Furthermore, aAR-NV retains the inherent immunostimulatory properties of DCs, facilitating T cell activation and enhancing cytotoxic T lymphocyte infiltration within tumor tissues. As a result, a synergistic effect has been observed in boosting T cell-based immunotherapy by simultaneously enhancing T cell activity and reducing its exhaustion. Our study using aAR-NV to antagonize androgen effects offers a promising new strategy for enhancing melanoma immunotherapy.
Enhancement of carbon monoxide catalytic oxidation performance by co-doping silver and cerium in three-dimensionally ordered macroporous Co-based catalyst
Cui B, Hu M, Zhou K, Li Y, Zhao T, Xiao M, Shao Z and Zhao M
Carbon monoxide (CO) catalytic oxidation offers an effective solution for environmental pollutant; however, its progress is limited by sluggish kinetics, and efficient catalysts remain scarce. Herein, we prepared Ag-Ce co-doped three-dimensionally ordered macroporous (3DOM) Co-based catalysts through the synergistic approach of co-doping and morphology control, systematically investigating their CO catalytic oxidation mechanisms. The appropriate amount of Ag-Ce co-doping maintained the original 3DOM structure, promote the mass transfer and diffusion of CO, promoted the redox capacity by increasing the ratio of Co to surface reactive oxygen species (O/ O), achieving low temperature conversion of CO. Specifically, concentration of Co is promoted via Co + Ag → Ag + Co and then combining the generated the active oxygen specie reduce the CO conversion temperature (Co + O/ O + CO → CO + Co). Among them 3D-5 %AgCoCe exhibited a lower activation energy (E) and T, which were only 48.79 KJ mol and 76.8 °C, respectively. Theoretical calculation indicated that the synergistic of co-doped system can lower down the O dissociation energy barrier by 0.242 eV compared with 3D-CoCe, thus facilizing the generation of active oxygen species and improving the oxidation kinetic of CO. This work innovated the preparation method of 3DOM co-doped system and provided opportunities to design high-performance heterogeneous catalysts.
Bifunctional gel coating for stabilizing zinc metal anodes in aqueous zinc-ion batteries
Liu Z, Qiu J, Yuan T, Zhang X, Bai S, Chen J, Chen S and Zhang Y
Currently, the zinc anode faces significant challenges such as dendrite growth, corrosion, and hydrogen evolution, which severely limit the practical applications of aqueous zinc-ion batteries. To address these issues, this study designed a zinc anode (denoted as CG@Zn) coated with a gel composed of carboxymethyl cellulose sodium (CMC) and glucose. This coating featured dual functionalities: it regulated the directional transport of Zn ions and constrained the electrochemical activity of interfacial water molecules, effectively inhibiting the growth of zinc dendrites and significantly reducing the occurrence of corrosion and hydrogen evolution side reactions. Benefiting from these advantages, CG@Zn exhibited excellent electrochemical performance. Under testing conditions of 5 mA cm/1 mAh cm, the symmetric battery assembled with CG@Zn demonstrated over 1000 h of stable cycling, achieving a cycle life five times that of bare zinc electrodes. Furthermore, the full cell configuration of CG@Zn//NaVO·1.5HO with a matching zinc sulfate electrolyte maintained a capacity retention of 67.1 % after 15,000 cycles at 10 A g, significantly outperforming the rapid capacity decay observed in bare zinc batteries under the same conditions. Therefore, this study successfully developed an effective bifunctional gel coating for zinc anodes using CMC and glucose, paving the way for the development of safe and eco-friendly aqueous zinc-ion batteries.
Enhancing CO tolerance via molecular trapping effect: Single-atom Pt anchored on MoC for efficient alkaline hydrogen oxidation reaction
Yang X, Yu W, Zhang Y, Qiao C, Liu L, Zhang Y, Li Q, Mou M, Wang R, Yuan X, Wang Z, Yan L and Zhao X
Developing highly efficient, stable, and CO-tolerant electrocatalysts for hydrogen oxidation reaction (HOR) remains a critical challenge for practical proton/anion exchange membrane fuel cells. Here in, an atomically dispersed platinum (Pt) on MoC nanoparticles supported on nitrogen-doped carbon (PtMoC-NC) with a unique yolk-shell structure is presented as a highly efficient and stable catalyst for HOR. The PtMoC-NC catalyst demonstrates remarkable HOR performance, with a high exchange current density of 2.7 mA cm and a mass activity of 2.15 A/mg at 50 mV (vs. RHE), which are 1.5 and 18 times greater than those of the 40 % commercial Pt/C catalyst, respectively. Furthermore, the unique PtMoC-NC structure exhibits superior CO tolerance at H/1,000 ppm CO, significantly outperforming commercial Pt/C catalysts. Density functional theory (DFT) calculations indicate that the introduction of MoC forms a strong electronic interaction with Pt, which decreases the electron density around the Pt atoms and shifts the d-band center away from the Fermi level. This results in a reduction of the *H adsorption energy and an optimization of the *OH adsorption energy in PtMoC-NC. In addition, by calculating the CO adsorption energy, it was found that MoC exhibits strong CO adsorption ability, which generating a molecular trapping effect, thereby protecting the Pt active sites from poisoning. The strong metal-support electronic interaction significantly enhances the catalytic activity, stability, and CO tolerance of the material, providing a new strategy for developing catalysts with these desirable properties.
Engineering cycling of Cu/Cu pairs in BiWO nanoflowers for boosting photocatalytic CO reduction
Ai L, Liu Z, Zhang X, Wang L, Jia D, Guo N, Zha M and Tan C
The photocatalytic reduction of CO represents an effective method for addressing environmental and energy crises. However, the slow migration and rapid recombination of photogenerated carriers have been identified as significant limitations on the efficiency of this process. Herein, we developed the cycling of Cu/Cu pairs in BiWO nanoflowers for boosting photocatalytic CO reduction. Cu is an electron trap that captures electrons to generate Cu, and Cu is unstable and prone to losing electrons to generate Cu in BiWO. The two processes are in concert to realize Cu/Cu cycling, which alters the charge transfer pathway and enhances the effective separation of photogenerated carriers for CO photoreduction reaction. Consequently, Cu-modified BiWO exhibited remarkable photocatalytic performance with the rate of CO and CH production reaching 165.28 and 16.49 μL·g in 3 h, which are 3.34 and 11.53 times that of the pristine BiWO. And the *COOH is the key to triggering the conversion of CO to CO, and *OC-CHOH is the key to forming CH by CC coupling. This work elucidates a dynamic copper valence cycling mechanism, establishing a paradigm for rational design of Cu-modified photocatalysts in solar-driven CO conversion.
Skin-adaptable, highly stretchable, and self-debonding hydrogel dressings for accelerating infected wound healing without secondary damage
Liu Y, Tang L, Ma Q, Shen Y, Zhao H, Liu X, Lin D and Zhou G
Damaged skin is highly susceptible to bacterial infections, often leading to subsequent inflammation. Although hydrogel dressings have been shown to address these issues, many exhibit inadequate wet adhesion, flexibility, and pain-free removability. These shortcomings may result in bleeding and further damage during dressing changes. To overcome these limitations, a stretchable and controllable adhesive hydrogel has been developed to facilitate the healing of infected wounds. This hydrogel incorporates molybdenum disulfide nanotubes coated with a tannic acid-iron complex (MoS@TA/Fe NTs) into a copolymer network composed of acrylic acid, 1-vinylimidazole, and N-succinimidyl acrylate. Hydrogen bonding between imidazole and carboxyl groups enhances the stability and tensile strength of the hydrogel. The hydrogel exhibits outstanding mechanical properties, enabling close adhesion to wet tissues. The imidazole groups interact with zinc ions, allowing for tunable adhesion, thereby effectively mitigating secondary damage upon dressing removal. Furthermore, the imidazole moieties disrupt bacterial cell membrane permeability, which, in combination with the photothermal antibacterial activity of MoS@TA/Fe NTs, effectively eradicates wound infections. The nanozyme-like activity of MoS@TA/Fe NTs scavenges excess reactive oxygen species (ROS) in the wound microenvironment. The hydrogel dressing promotes neovascularization and accelerates collagen deposition at the wound site, thereby significantly enhancing wound healing. Consequently, this multifunctional hydrogel exhibits great potential in the treatment of infected wounds.
Amorphous high-entropy phosphate as passivation layer by inhibiting adsorption of chloride ions toward highly durable self-supporting electrode for enhanced seawater electrolysis
Zhang Q, Song Y, Liu Q, Zhao F, Gao T, Yang X, Zhu J, Yang S, Chen L, Li S, Feng W and Zhao P
Seawater electrocatalysis is an attractive technique for sustainable energy production, but the challenge of catalyst corrosion by Cl and stability needs to be addressed. High-entropy alloys (HEAs) attracted much attention for energy conversion in seawater electrocatalysis, due to high strength, stability, and corrosion resistance. Herein, the bilayered CrCoNiFe-P electrode composed of CrCoNiFe alloy substrate and phosphate modification layer (30 nm) is constructed by using vacuum arc-melting and anodic oxidation methods. The amorphouslike phosphate layer (30 nm) not only acts as a passivation layer, enhancing the corrosion resistance and inhibiting the Cl adsorption, but also acts as the catalytic active layer, enhancing the catalytic performance. Theoretical studies demonstrate that the PO doping optimizes the d-band structure, reduces the free energy of the rate-determining step and inhibits adsorption of Cl. Benefiting from the bilayered structure and constructed surface, for oxygen evolution reaction (OER), the overpotential required to reach 10 mA cm is only 290 mV. In addition, During the long-term testing at 10 mA cm, the potential presents only decreased by 2.7 % after 350 h in 1 M KOH with 0.5 M NaCl. The voltage of CrCoNiFe-10||Pt to reach 10 mA cm is only 1.522 V. These findings offer a facile strategy for electrodes with high corrosion resistance and catalytic activity for energy conversion in seawater.
Incorporating nickel-substituted polyoxometalate into a photoactive metal-organic framework for efficient photodegradation of thiamethoxam insecticide
Lu BB, Zhao QY, Lu JC, Chen ZL, Wang R, Kong XC, Yu JH, Fu Y and Ye F
Hydrogen bonding enhances the interactions between host and guest molecules and facilitates electron transfer between them. In this study, a series of hydrogen-bonded Z-scheme photocatalysts were prepared via impregnation. Nickel (Ni)-substituted polyoxometalate (POM) NaK[Ni(HO)(PWO)]∙32HO (NiP) was anchored within the pores of Zr(μ-OH)(-OH)(TBAPy) (NU-1000) via hydrogen bonding interactions (HTBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene). Hydrogen bonding not only effectively prevented the leakage of NiP from NU-1000 pores but also facilitated electron transfer from NiP to NU-1000. The optimized 0.3-NiP@NU-1000 photocatalyst delivered remarkable performance toward thiamethoxam (TMX) photodegradation, achieving a degradation efficiency of 75.1 % after 120 min. The effects of the photocatalyst dose, pH, coexisting ions, and water sample on TMX degradation were investigated. Radical scavenging experiments and electron spin resonance data revealed that superoxide radicals and holes are the primary species responsible for photodegradation. Moreover, the reaction mechanism and degradation pathways of TMX were thoroughly investigated. Density functional theory calculations confirmed that TMX is adsorbed onto NiP via hydrogen bonding, structurally changing TMX and increasing its susceptibility to degradation. Chia seed growth experiments and Toxicity Estimation Software Tool analysis indicated that the aquatic toxicities of TMX intermediates and final products are lower than that of the undegraded TMX. This study advances the application of substituted POM-modified NU-1000 for treating TMX-contaminated wastewater.
High-entropy engineering enables O3-type layered oxide with high structural stability and reaction kinetic for sodium storage
Wang X, Kang Q, Sun J, Yang Z, Bai Z, Yan L, Meng X, Wan C and Ma T
O3-type layered oxides are considered promising cathode materials for sodium-ion batteries (SIBs) due to their high theoretical capacity, but they often face issues with structural instability and poor sodium-ion diffusion, leading to rapid capacity fading. In this work, we introduce a high-entropy approach combined with synergistic multi-metal effects to address these limitations by enhancing both the structural stability and reaction kinetics. A novel O3-type layered high-entropy cathode material, NaFeCoNiMnTiO (TMO5), which was synthesized via a straightforward solid-phase method for easy mass production. Experimental analysis combined with in/ex-situ characterization verifies that high-entropy metal ion mixing contributes to the improved reversibility of the redox reaction and O3-P3-O3 phase transition behaviors, as well as the enhanced Na diffusivity. Benefit from the advantage of structure and composition, the TMO5 exhibits a higher initial specific capacity of 159.6 mAh g and an impressive capacity retention of 85.6 % after 100 cycles at 2 C with the specific capacity of 110.1 mAh g. This work showcases high-entropy O3-type layered oxides as a promising pathway for achieving robust, high-performance SIB cathodes.
Interface-driven energy filtering effect and enhanced thermoelectric performance of AgSe/SnS composites: An experimental and theoretical insights
Santhosh R, Kamalakannan S, Harish S, Archana J, Ponnusamy S and Navaneethan M
This study examined the thermoelectric (TE) and mechanical properties of n-type AgSe/SnS nanocomposites synthesized via hydrothermal methods and hot-press densification. The incorporation of SnS nanosheets into the AgSe matrix enhanced the thermoelectric performance, achieving a maximum figure of merit (zT) value of 0.91 at 393 K for the sample with 2.5 wt% SnS, representing a 13 % improvement over that of AgSe. This enhancement is attributed to an increased power factor (∼2704 μWm K at 393 K) resulting from band convergence and a reduced thermal conductivity (κ ∼ 0.744 Wm K at 303 K) owing to interfacial phonon scattering. Furthermore, the nanocomposites exhibited enhanced mechanical properties, with Vickers hardness increasing by up to 28 % compared to that of AgSe. Density functional theory (DFT) calculations were employed to assess the structural and electronic properties of AgSe and AgSe/SnS nanocomposites. The computed bandgap confirmed improved electrical conductivity, whereas the binding energy and electron density difference analyses elucidated the interaction strength and charge transfer in the nanocomposite. These findings elucidate the potential of AgSe/SnS nanocomposites as promising thermoelectric materials for room-temperature applications and demonstrate the efficacy of nanostructuring in enhancing thermoelectric and mechanical properties.
Engineering a dual Z-scheme copper oxide/boron carbon nitride/MXene heterojunction with tailored band alignment for high-efficiency photocatalytic degradation of refractory organic pollutants
Mutahir S, Khan MA, Liu W, Butt R, Humayun M, Meng L and Shaheen I
The accumulation of persistent environmental pollutants presents significant risks to ecosystems and human health, requiring immediate removal and effective control as a pressing global concern. Herein, we report the design and fabrication of graphitic carbon nitride (g-CN) based dual Z-Scheme heterojunction for effective photocatalytic degradation of various refractory pollutants in wastewater. Firstly, we synthesized boron-doped g-CN via the direct calcination of melamine along with boric acid, and then coupled with Copper Oxide (CuO) and MXene via the wet-chemical method to fabricate dual Z-scheme CuO/BCN/MXene composite. The physicochemical features of the as-prepared CuO/BCN/MXene composite and reference samples were investigated via various characterization techniques. The photocatalytic degradation performance and the kinetics study for malachite green was evaluated using the as-fabricated dual Z-scheme composite and the coupling components. The CuO/BCN/MXene composite revealed exceptional photocatalytic performance by achieving 98.3 % degradation for malachite green, which is remarkably higher than the reference samples. The enhanced performance was attributed to the band gap narrowing, extended light absorption, and improved charge carrier separation. This study will provide new insights into the design and fabrication of functional nanomaterials for efficient photocatalytic degradation of pollutants and other applications.
Atomic spin engineering of Fe-N-C by axial chlorine-ligand modulation for lightweight and efficient electromagnetic wave absorption
Wei Q, Zhang P, Guo X, Jiang W, Tao X, Shen PK and Tian ZQ
Introducing atomic magnetic factors to regulate the electromagnetic parameters of graphene is essential to achieving new-generation electromagnetic wave (EMW) absorbing materials. Herein, a new strategy of endowing graphene with atomic magnetic moments was developed by implanting high-spin FeN moieties with axial Cl ligands into 3D N-doped graphene (Cl-Fe-NG). The design facilitates the multi-reflection loss, dielectric loss and magnetic loss of EMW at ultra-low filling. Its minimum reflective loss (RL) is up to -65.9 dB with the biggest effective absorption bandwidth (EAB) of up to 5.5 GHz in the thin thickness of 1.9 mm and a low filler loading of 5 wt%. Meanwhile, a waterborne polyurethane wave-absorbing coating filled with 5 wt% Cl-Fe-NG demonstrates its high absorption performance with a dominant absorption loss of 90 %. Additionally, theory calculations reveal that introducing axial Cl-ligand FeN moiety with high-spin Fe into graphene not only generates additional electric dipoles but also induces an atomic magnetic moment, effectively enhancing the dielectric and magnetic loss of graphene for EMW absorption. This work provides a new approach to designing graphene with atomic magnetic moments for developing EMW absorbing materials with "thin, wide, light, and strong" characteristics instead of the conventional route of graphene with magnetic nanoparticles.