Latest ArticlesGuest molecule intercalation is an effective strategy for engineering electron structures and enhancing photocatalytic CO2 reduction. Our designed charge-transfer system incorporates 28 nuclear H2O molecules as electron mediators within the POM-based photocatalyst, enabling efficient electron transport pathways. Comparative analysis of synthesized isostructural catalysts shows water-intercalated Na7[Co2(H2O)8(H11CoP8Mo12O62)]·44H2O (abbr. compound 1) achieves exceptional CO2 reduction activity (21,347.4 µmol g-1 h-1), outperforming anhydrous (C4H14N2)4[Co2(H10CoP8Mo12O62)]·4H2O (abbr. compound 2) by 68%. This work demonstrates that water intercalation simultaneously optimizes band structure and improves material stability, providing a novel paradigm for advanced photocatalytic system design.
Achieving higher proton conductivity of proton-conducting materials in solid-state is one of the utmost challenges in materials science. Due to their oxygen-rich structure and negative surface charge, polyoxometalates (POMs) anions have high requirements for proton carrier density and proton mobility, and thus have great potential as proton conducting materials. Furthermore, the versatility in modifying the ligand environment or incorporating acidic functional groups in POMs allows for precise tuning of their proton conductivity and stability under operational conditions. Therefore, it is an effective strategy to select a suitable organic ligand to stabilize the [TeMo6O21]2- anion assembled in-situ by covalent modification. In this paper, three [TeMo6O21]2- anionic clusters have been designed and synthesized by using polydentate phosphonate ligands and guided by transition metals, H26[Co6{N(CH2PO3)2(CH2COO)}6(TeMo6O21)4(H2O)8]·64H2O (complex 1), H26[Cu6{N(CH2PO3)2(CH2COO)}6(TeMo6O21)4(H2O)6]·78H2O (complex 2) and H34Na2[Co8{N2(CH2)2(CH2PO3)3(CH2PO3H2)}4(TeMo6O21)6(PO3)4(H2O)16]·84H2O (complex 3). Among them, complexes 1 and 2 are isomorphic, and complexes 1–3 have good proton conduction properties, resulting in values of 1.3 × 10−2, 1.22 × 10−2, and 1.11 × 10−2 S/cm, respectively (75% relative humidity, 80 ℃). This work offers a promising strategy for the development and design of novel telluromolybdate clusters suitable for proton conductive materials.
Integration of redox ability and conductivity in binder is highly desirable to maximize their functions for high-performance battery requirements. Here, a novel redox covalent organic polymer binder (TTF-COP) has been developed by in-situ polymerizing redox/conductive tetrathiafulvalene unit and adhesive thiourea unit. TTF-COP can achieve one-pot cathode fabrication and simultaneously provide strong interactions with cathodic materials, showing significantly enhanced mechanical strength of the electrode, accelerated capture/conversion of lithium polysulfides (LiPSs), about 10,000 times higher viscosity (at shear rates of 0.1–1 s-1), and about 200 times enhanced electrical conductivity than that of PVDF. TTF-COP based cells exhibit high initial capacity (1126 mAh/g at 0.5 C, 928 mAh/g at 1 C, 611 mAh/g at 5 C, respectively) and excellent cycling stability over 800 cycles at 5 C (0.089% decay per cycle). Moreover, the cell shows an excellent specific capacity of 5.1 mAh/cm2 under a high sulfur loading of 7.1 mg/cm2 and low E/S ratio of 10.7 µL/mg. This work provides a new reference for designing multifunctional binders, hoping to enrich the binding chemistry for sustainable battery targets.
In this work, we report the controllable synthesis and characterization of four atomically precise silver clusters, Ag18(SbW9O33)2(DPPP)8 (1, DPPP = 1,3-bis(diphenyphosphino)propane), Ag18(SbW9O33)2(DPPB)8 (2, DPPB = 1,4-bis(diphenylphosphino)butane), Ag18(SbW9O33)2(DPPPe)8 (3, DPPPe = 1,5-bis(diphenylphosphino)pentane), and Ag18(SbW9O33)2(TPP)14 (4, TPP = triphenylphosphine) by using a facile one-pot solvothermal approach. The resulting four Ag clusters exhibit similar lacunary [SbW9O33]9‒ ({SbW9O33})-sandwiched structures, which can be adjusted by the external different phosphine ligands. In addition, all four clusters display variable physicochemical and catalytic performance, correlating well to their distinct molecular structures.
Lithium-metal batteries (LMBs) are promising next-generation high-energy-density systems due to lithium's high theoretical capacity. However, while ester-based electrolytes support high-voltage cathodes, their poor compatibility with lithium metal hinders progress. In this study, a porous material with sub-nanochannels was constructed on lithium metal, inducing a pre-desolvation process that promotes a highly aggregative nano-confined electrolyte. This design mitigates solvent-lithium reactivity, enabling dendrite-free deposition and a stable LiF-rich solid electrolyte interphase (SEI). As a result, NCM-811//Li (LiNi0.8Co0.1Mn0.1O2//Li) cell achieved exceptional cycling stability (89.2% capacity retention after > 400 cycles). This strategy provides a viable pathway for advanced high-energy-density batteries.
Although the incorporation of fillers has improved the high temperature (150–200 ℃) capacitance of polymer composite dielectrics, effective strategies for designing filler-matrix interface structures remains a formidable challenge. Herein, defect-rich nanosheets (Ca2Nb2.75Ti0.25O10, CT) were coated with a zeolite imidazolate frameworks-8 (ZIF-8, Zn(C4H5N2)2) layer (mCT). The mCT was integrated into polyetherimide (PEI) to create the polymer-based dielectrics. The defects on the surface of the negative CT nanosheets exhibited strong anchoring effects on the Zn2+ in ZIF-8, enhancing the filler-coating layer interface. Additionally, X-ray absorption fine structure analysis and density functional theory confirmed that the porous ZIF-8 coating layer forms strong coordination bonds with the PEI molecular chains, thereby an increased band gap (3.3 eV) of PEI/mCT compared to PEI (3.0 eV). It demonstrated exceptional performance at high temperatures, achieving ultra-high energy storage densities of 5.25 and 4.47 J/cm3 with efficiency > 90% at 150 and 200 ℃, which are higher than PEI (0.4 and 0.4 J/cm3). This work offers a new approach and reference for designing high-temperature polymer composite dielectrics for energy storage applications.
Li-S batteries (LSBs) offer significant promise for next-generation energy storage systems on account of their high energy density and the high capacity of sulfur. Nevertheless, the severe shuttle effect of lithium polysulfide (LiPSs) and the sluggish reaction kinetics greatly hinder the further application of LSBs. In this manuscript, Hollow CeOx/CoS core-shell hybrid were designed and synthesized using ZIF-67 as the self-template to prepare hollow CoS dodecahedral nanoboxs and the subsequent generation of CeOx nanodots. When used as the polyolefin separator modifier, the unique dodecahedral structure of hollow CoS/CeOx presents large specific surface area, abundant porous structure and enough active sites, which not only ensures the fast transport of electrolyte/ions and offers numerous active catalytic sites to accelerate the reaction kinetics of LiPSs. In addition, the catalytic activity of the CeOx/CoS hybrid greatly enhance the uniform ion diffusion and stable growth of lithium nucleation on the lithium metal anode side. The cell with CeOx/CoS modified separator presented excellent long cycle stability and satisfactory rate performance. The battery can maintain the capacity of 502.2 mAh/g after 900 cycles at the current density of 1 C, accompanying by a minimal 2 decay rate of 0.057%. Even at a current density of 3 C, a high specific capacity of 735.58 mAh/g can still obtained. Besides, when the sulfur loading increase into 4.480 mg/cm2, the battery still can maintain excellent cycling stability with the capacity retention ratio of 94.5% after 100 cycles. This study will provide new strategy for the design and preparation of heterostructure with outstanding catalytic performance for LSBs.
Bromine, a vital industrial chemical raw material with extensive applications, faces extraction challenges from diluted underground brine due to high energy consumption and low efficiency in conventional methods. In this study, we introduce a CO2 activation of acid-thermal treated graphite felt (AHGF-Y) as a highly effective negative electrode for bromine extraction, achieving remarkable efficiency exceeding 90%. With enriched oxygen-containing functional groups introduced by CO2 activation serving as active sites, the engineered bromine extraction electrodes demonstrates superior bromine oxidation reaction (BrOR) under high Cl/Br ratio conditions. Coupled with hydrogen production, in electrolyte with a Cl/Br ratio of 38, AHGF-Y operated at a low overpotential and achieved remarkable bromine extraction efficiency (94%), with minimal energy consumption (1.61 kJ/g). Notably, when applied to underground brine with high Cl/Br ratio of 255 and multiple interfering ions, AHGF-Y maintained extraction efficiency of 95.5%, significantly outperforming other reported works. Furthermore, AHGF-Y achieved an near-unity Faradaic efficiency (F.E.) of up to 99.7% in a scale-up hydrogen-bromine flow cell (HBFC), enabling simultaneous bromine extraction and hydrogen production. These results highlighted the potential of AHGF-Y as a sustainable and efficient material for large-scale bromine extraction from underground brine.
Layered V5O12·6H2O is a cathode material with great development potential for aqueous zinc-ion batteries due to its large interlayer spacing (~1.18 nm), high proportion of V4+, and abundant interlayer H2O. However, its low electronic conductivity and poor lattice stability lead to significant capacity degradation. In this regard, we develop a synergistic pre-intercalation & coating engineering, where Ni2+, Mn2+, or Zn2+ cations are pre-intercalated by one-step hydrothermal approach, and graphite oxides (GO) are coated by an electrostatic self-assembly strategy. It is found that Zn2+ pre-intercalation shows a better enhancement effect on the Zn2+/H+ storage reversibility and stability, and the charge and mass transfer kinetics. Meanwhile, the synergistic effect of Zn2+ pre-intercalation and GO coating achieves the enhancement of the cycling performance and rate capacity with the minimal loss of initial capacities, where the discharge capacity of 288.3 and 183.3 mAh/g with the retention of 85.0% and 61.6% are achieved at 1 and 3 A/g after 150 and 600 cycles, respectively. The excellent electrochemical performance is attributed to the biggest downward shift of the p-band center of oxygen, the moderate radius of Zn2+, and the coating of ultrathin GO with high electrical conductivity.
The sluggish dynamics of photogenerated carriers and low sunlight absorption rate severely impede the performance of ZnIn2S4-based photocatalysts. To enhance their photoactivity, Sv-ZnIn2S4@AgBiS2 (Sv-ZIS@ABS) heterostructure composites with sulfur-rich vacancies were synthesized by growing ZnIn2S4 nanosheets on the surface of AgBiS2 through a one-step solvothermal method. The results demonstrate that the Sv-ZIS@ABS composites possess a substantially larger specific surface area and remarkable photocatalytic performance, achieving a hydrogen evolution rate of 4560.2 µmol h-1 g-1, approximately 14.27 times higher than that of pristine ZIS. The electron transfer kinetics in the ZIS@ABS heterojunction were thoroughly investigated using photoluminescence (PL), charge differential density, kelvin probe force microscope (KPFM), and in situ XPS, etc. Based on photocatalytic H2 evolution experiments and density functional theory (DFT) calculations, a plausible photocatalytic mechanism for the Sv-ZIS@ABS composites was proposed. This study provides valuable insights into the design of highly efficient transition metal sulfide-based heterojunction photocatalysts, with a focus on optimizing electron transfer kinetics in these semiconductor materials.
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