Latest ArticlesThe development of high-performance nonlinear optical (NLO) crystals for the short-wave ultraviolet (UV) region remains a significant challenge. In this work, four novel organic-inorganic metal halides, (3-QUO)2MX4 (3-QUO = 1-azabicyclo[2.2.2]octan-3-one; M = Zn, Cd; X = Br, I), were developed. Our initial efforts with the iodide compounds, (3-QUO)2ZnI4 and (3-QUO)2CdI4, yielded materials with modest second-harmonic generation (SHG) responses and, critically, they were non-phase-matchable. To overcome this, we employed a halogen-substitution strategy, replacing iodine with bromine, guided by the principle of bandgap widening. This approach successfully yielded (3-QUO)2ZnBr4 and (3-QUO)2CdBr4, which exhibit superior short-wave UV transparency and achieve phase-matchable SHG. Specifically, (3-QUO)2ZnBr4 shows a wide bandgap of 5.10 eV (UV cutoff: 220 nm) and a phase-matchable SHG response of 1.5 times that of KH2PO4 (KDP). Similarly, (3-QUO)2CdBr4 possesses a bandgap of 4.55 eV (UV cutoff: 245 nm) and an SHG response of 1.8 × KDP. Furthermore, these materials exhibit yellowish-white fluorescence under blue light excitation. This work demonstrates an effective approach to simultaneously tune bandgap, SHG response, and phase-matching capabilities for short-wave UV NLO applications.
Environmental remediation demands efficient strategies for antibiotic degradation. Herein, we report the successful selective loading of nano zero-valent iron (nZVI) into the lumen of halloysite nanotubes (HNTs) via vacuum-assisted infusion and thermal reduction (denoted as nZVI@HNTs). This confined nanoreactor architecture simultaneously acts as a robust reductant and a Fenton-like catalyst. The tubular structure of HNTs enhanced nZVI dispersion and stability while leveraging its nanoconfinement effect to concentrate pollutants and suppress parasitic reactions between nZVI and H2O2. For tetracycline (TC) degradation, the nZVI@HNTs+H2O2 system achieved 86.61% removal within 90 min (20 mg/L TC, pH 5.5), outperforming surface-loaded controls by >19%. Crucially, the HNT lumen provides dual protection: Spatial isolation suppresses non-target nZVI consumption by O2/H2O, while constrained diffusion delays H2O2 contact, prioritizing contaminant reduction before controlled Fe2+-activated oxidation. Reactive oxygen species (ROS), including ·OH, ·O2−, and 1O2, synergistically drove TC degradation through radical and nonradical pathways. LC-MS analysis identified intermediates formed via demethylation, ring opening, and hydroxylation, with toxicity assessments confirming reduced acute toxicity, mutagenicity, and developmental toxicity of byproducts. Notably, nZVI@HNTs retained 64.03% efficiency after five cycles, demonstrating superior reusability. This work provides a novel strategy to enhance nZVI’s environmental applicability by combining confinement engineering with redox-coupled processes, offering broad prospects for sustainable water purification.
Aqueous polysulfide/iodide redox flow batteries (SIRFBs) have been identified as a promising solution for scalable energy storage, exhibiting high energy density and cost-effectiveness, attracting considerable attention. Nonetheless, their practical applicability hindered by the suboptimal redox reaction kinetics, leading to constrained energy efficiency (EE) and power density. Herein, this study proposes a novel approach for coupling of graphene oxide with abundant sulfur vacancies in MoS2 nanosheets (VS-MoS2@GO). The bifunctional catalysts enhancing the transformation of S2−/Sx2− and I−/I3− redox couples while concomitantly improving the reaction kinetics. The experimental and theoretical calculation analyses elucidate that the GO bond with VS-MoS2 induces C-O-Mo and results in generating abundant sites, which attribute to the enhanced adsorption of crucial reaction intermediates and improved charge transfer. Consequently, the SIRFB derived notable EEs of 95.4%, 90.2%, and 75.6% at 10, 20, and 50 mA/cm2 with 50% state of charge, respectively. Furthermore, these batteries exhibit remarkable power density (93.2 mW/cm2), ultralow overpotential (100 mV), and an extended cycling life that exceeds 500 cycles. This work presents an innovative perspective to design high-active electrode materials that have potential for broad application in sundry flow battery chemistry, which would facilitate technological breakthroughs and advancements in the field of RFB.
Biomass-derived hard carbons (HCs) have emerged as highly promising anode materials for sodium-ion batteries (SIBs), owing to their high reversible capacities as well as low cost. However, the complex internal structure of biomass precursors presents significant challenges for precise control of microstructure as well as energy storage performance of the final HC products. To address this issue, in this study, three anthraquinone (AQ)-based organic small molecules, namely AQ, 2,6-dihydroxyanthraquinone (DQ) and 2,6-diaminoanthraquinone (DAAQ), are selected as crosslinking agents of bamboo biomass, to reveal the unique role of functional groups in these molecules for the precise regulation of microstructure of the bamboo-derived HCs. The results demonstrate that, under the same aromatic carbon skeleton, hydroxyl and amino groups have significant influence on the pore structure, graphitization degree, and electrochemical performance of HCs. Among them, DAAQ with amino functional groups exhibits the best crosslinking efficiency, resulting in a more ordered carbon structure along with successful N-heteroatom doping. Consequently, the HC prepared from DAAQ-crosslinked bamboo achieves a remarkable reversible capacity of 351 mAh/g and a high initial Coulombic efficiency of 86.4% at 20 mA/g. This work demonstrates the significant potential of functionalized AQ-based molecules as efficient crosslinkers in regulating the microstructure of biomass-derived HCs.
Lithium metal batteries are widely recognized as a promising candidate for next-generation energy storage systems due to their exceptional theoretical energy density. However, the uncontrollable dendritic growth of lithium metal anodes remains a critical safety hazard, significantly impeding their practical implementation. The unique open-channel structures and functional moieties within metal-organic framework (MOF)-based solid-state electrolytes enable precise regulation of lithium-ion transport, offering a novel approach to address the lithium dendrite issue. This review systematically summarizes recent advances in MOF-based solid-state electrolytes that are categorized into three representative systems: pristine MOF-based electrolytes, MOF/ionic-liquid hybrid electrolytes, and MOF/polymer composite electrolytes. The discussion focuses on design principles and ion conduction mechanisms of MOF-based solid-state electrolytes, emphasizing the correlation between structural features and electrochemical performance. Furthermore, prospects for MOF-based electrolytes are discussed, highlighting future research directions towards high-performance MOF-based electrolytes for lithium metal batteries with high safety and high energy density.
Spin crossover (SCO) metal-organic frameworks (MOFs) exhibit significant potential for applications in data storage, displays, switches, actuators and sensors. However, designing novel SCO MOFs with new framework topologies remains a considerable challenge. Herein, the self-assembly of FeBr2 and Fe(ClO4)2·6H2O with K[Ag(CN)2] and N1,N1,N3,N3-tetra(pyridin-4-yl)benzene-1,3-diamine (i-TPBA) resulted in two distinct MOFs: [FeⅡ3{Ag8Br8(CN)6}(i-TPBA)3]·4DEF (1, DEF = N,N-diethylformamide) and [FeⅡ{Ag(CN)2}(i-TPBA)]ClO4·2H2O·0.5DEF (2). In 1, the hexatopic cluster anions [Ag8Br8(CN)6]6−, tetratopic ligands i-TPBA and hexatopic Fe(Ⅱ) ions are linked to form a cluster-based MOF with the urk topology. In contrast, the [Ag(CN)2]− units in 2 axially bridge the Fe(Ⅱ) ions, constructing one-dimensional right-handed 31 helical chains, which are further linked by tetratopic i-TPBA connectors to generate a three-dimensional chiral framework with a previously unreported topology, designated as sco1. Moreover, the SCO behavior can be effectively modulated by thiophene guest molecules, leading to the observation of a rare scan rate-dependent hysteretic SCO behavior in 2_thio. Thus, this study demonstrates that multidentate ligands can be employed to construct SCO MOFs with new topologies, offering a versatile platform for the advancement of multifunctional SCO materials
The large-scale deployment of proton-exchange membrane water electrolysis (PEMWE) is plagued by the exclusively rely on Ir for anode water oxidation. Platinum (Pt), as one of the few acid stable elements, has long been ignored as a possible alternative due to its surface oxidation and passivation. In this study, we incorporate boron (B) and strontium (Sr) into Pt to achieve notable promotion in catalytic activity and long-term anti-passivation feature. While B serves as an electron reservoir by donating charge to Pt sites, Sr induces compressive strain to suppress lattice oxygen formation. The synergistic effects of B and Sr effectively modulate Pt-O orbital coupling from oxidative passivation and confer the best water oxidation activity and stability. Notably, the B,Sr-Pt catalyst achieves a low overpotential of 308 mV at 10 mA/cm2 in 0.5 mol/L H2SO4, approaching those of the Ir based catalysts. In PEMWE devices, B,Sr-Pt exhibits an operating voltage of 2.061V at 1 A/cm2 and operate stably for 240h at 1 A/cm2. These findings offer a promising strategy for enhancing the OER efficiency and durability of Pt-based catalysts by effectively addressing Pt site passivation.
Advancing low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media is essential for sustainable hydrogen production, particularly in the context of anion exchange membrane (AEM) water electrolysis systems. Among various candidates, cobalt-based phosphides, particularly CoP, have drawn significant attention as cost-effective alternatives to platinum-based HER electrocatalysts due to their excellent catalytic performance. However, improving both water dissociation kinetics and hydrogen adsorption free energies remains a challenge. In this study, we introduce lead (Pb), a non-transition metal with higher electronegativity and a similar ionic radius to Co, to modify the electronic structure of CoP at both Co and P sites. Pb doping significantly optimizes both water dissociation and adsorption free energy in the alkaline HER process. The optimized Pb-CoP/CC electrocatalyst reduces the overpotential from 100 mV to 53 mV and achieves a Tafel slope of 57 mV/dec in alkaline electrolyte. Additionally, it exhibits excellent durability, maintaining stable performance for over 120 h. The improved HER performance of Pb-CoP/CC can be ascribed to the synergistic interactions between its components: accelerated water dissociation on Co sites, optimized hydrogen intermediate adsorption on P sites, and improved charge transfer abilities. These findings are supported by experimental data and DFT calculations. When used as the cathode in an AEM electrolyzer, Pb-CoP/CC achieves a current density of 500 mA/cm2 at 1.95 V, demonstrating excellent stability. This work highlights the efficacy of metal ion doping with higher electronegativity in improving HER performance and establishes a versatile strategy for other non-precious metal-based transition metal compounds, paving the way for high-performance AEM electrolyzers.
Argyrodite sulfide solid electrolytes are highly favored by the researchers in the field of all-solid-state lithium metal battery due to their high ionic conductivity, relatively stable electrochemical window, and excellent processability. However, argyrodite sulfide solid electrolytes still face some technical difficulties that urgently need to be overcome, such as poor air stability and interface compatibility. This work reports a novel Li6+2xP1–xGaxS5–1.5xO1.5xCl (i.e., LPSC-xGa2O3) electrolyte via modifying Li6PS5Cl electrolyte with Ga2O3. The experimental results show that the prepared solid electrolyte has the highest ionic conductivity when the doping content of Ga2O3 reaches to x = 0.05. In addition, LPSC-0.05Ga2O3 has been proven to have good ability to suppress Li dendrites and improve cathode and anode interface compatibilities. The assembled all-solid-state lithium metal battery using LPSC-0.05Ga2O3 can maintain long-term stability for >200 cycles at 0.5 C. This work has laid the vital foundation for designing a high-performance solid-state electrolyte and promoting development of power battery industry.
Hydrazine oxidation reaction (HzOR) is highly thermodynamically favorable, but typically kinetically slow with a significant overpotential at most electrodes. Developing and illustrating a generic methodology for reducing the overpotential is of great significance but challenging. Here we designed a Fe-tannic acid (Fe-TA) buffering coating for carbon-hybridized Fe3O4 (C-Fe3O4) particles to reduce the overpotential of the multiple-proton-involved HzOR, which was further applied to highly efficient hydrazine-assisted hydrogen production and electrochemical hydrazine detection. A series of comparative experiments confirmed that the Fe-TA coating significantly reduces the isoelectric point, enhances the wettability, increases the electric double-layer capacitance, and decreases the charge transfer resistance, thereby lowering the resistance overpotential. Notably, C-Fe3O4@Fe-TA exhibited an excellent buffering effect that effectively decreases the concentration overpotential for electrochemical HzOR, which can be attributed to the reversible transformations among the mono-, bis-, and tris-complexes of Fe(Ⅲ) with tannic acid. Correspondingly, C-Fe3O4@Fe-TA achieved current density of 10 mA/cm2 at 23 mV (vs. RHE) in the electrolyte containing 1.0 mol/L KOH and 0.3 mol/L hydrazine. Coupled with HzOR, the C-Fe3O4@Fe-TA║Pt wire electrolysis system required a low working voltage of only 0.22 V at 10 mA/cm2 for synchronous hydrogen production, which was significantly lower than that of a traditional overall water splitting system (1.23 V). Moreover, C-Fe3O4@Fe-TA showed good performance in electrochemical hydrazine detection, simultaneously exhibiting high sensitivity (1478 µA L mmol−1 cm−2), a low detection limit (0.15 µmol/L), high selectivity, excellent stability, and high reliability for the analysis of real samples. This study reveals that the Fe-TA buffering coating can effectively decrease both the concentration and resistance overpotentials in electrochemical HzOR, demonstrating its potential as a general methodology for reducing the overpotential in this class of multiple-proton-involved reactions.
No. 86 Xueyuan South Road, Haidian District, Beijing
010-62662699(Operation and Technical Support)
qkjq@cast.org.cn
Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House
