Tubular g-C3N4/Cu3Mo2O9 (CNCM) heterojunction was synthesized via an ultrasound-assisted self-assembly strategy and applied for the photocatalysis-self-Fenton mitigation of algal blooms. The results demonstrate that the CNCM-0.20 sample achieved an algal inactivation efficiency of 96.23% within 2 h. Changes in properties such as decrease in the absolute zeta potential and increase in intracellular non-electrolyte content suggest disruption of algal cell structure and loss of cell membrane integrity. Characterization results confirm that CNCM-0.20 enhances the separation efficiency of photogenerated charges. Free radical trapping experiments further confirmed that ·O2- is the primary reactive species in the deactivation process, and that it generates H2O2 and converts to ·OH, forming a highly efficient photocatalysis-self-Fenton system. Density functional theory calculations revealed that the work function of g-C3N4 (4.20 eV) is substantially lower than that of Cu3Mo2O9 (7.61 eV). This disparity drives spontaneous interfacial electron migration from g-C3N4 to Cu3Mo2O9, giving rise to built-in electric field (IEF) and band bending. Results from charge density difference mapping and Bader charge calculations indicated that approximately 0.2 e of net charge was transferred across the interface. Subsequently, under light excitation, the migration of photo-generated electrons is hindered by band bending and the IEF, while holes migrate along the IEF direction. The charge transfer pathway was verified at the molecular level.

The sustainable supply of uranium attracts widespread attention in meeting the rising global demand for nuclear energy. Although seawater contains abundant uranium, uranium extraction from seawater is still challenged by the ultra-low uranium concentration and biofouling from marine microorganisms. Herein, a nitrogen-doped graphene oxide aerogel loaded with cobalt-based metal-organic frameworks (Co-MOF/GCN) is fabricated for efficient uranium extraction from seawater. This material exhibits excellent extraction performance and kinetics with a saturated adsorption capacity of 701.90 mg/g and an equilibrium time of 30 min. Furthermore, Co-MOF/GCN demonstrates a remarkable selectivity and antibacterial ability, which enables it to achieve a uranium extraction capacity of 10.05 mg/g from natural seawater in only 1 day. Meanwhile, Co-MOF/GCN is capable of partially reducing U(VI) to U(IV) alongside uranium adsorption, which is energy-efficient without the need for external energy sources such as light or an electric field. This work not only demonstrates the design of a high-performance, multifunctional material for uranium extraction, but also paves the way for its economically viable application in seawater.

The selective catalytic reduction of NO with NH3 (NH3-SCR) reaction is governed by the interplay of surface acidity and redox activity, yet the mechanism of their cooperation remains elusive. Herein, Ce-O-W linkages were constructed on Ce/ZrO2 to couple Ce4+/Ce3+ redox cycle with tungsten-derived acidity. Operando DRIFTS and transient experiments revealed that gaseous NO reacts directly with NH3 adsorbed on Lewis Ce4+ sites, following an Eley-Rideal pathway. Br & oslash;nsted acid sites from Ce-O-W acted as NH4+ reservoirs, dynamically replenishing Lewis-bound NH3 and sustaining continuous reactivity. Operando UV-vis spectroscopy confirmed that NO + NH3 exposure reduced Ce4+ to Ce3+, while O2 re-oxidized Ce3+ to Ce4+, establishing the redox cycle. Density functional theory calculations supported that NH3 dehydrogenation on Ce sites and subsequent coupling with gaseous NO were energetically favorable, while O2-assisted Ce3+ re-oxidation required the highest energy barrier. These results highlight the cooperative function of Ce-O-W acid-redox site in promoting SCR activity through dynamic L-NH3/B-NH4+ interplay and sustained Ce redox cycling.

The electroreduction of CO2 to CO is fundamentally hindered by sluggish COOH intermediate formation and the competing hydrogen evolution reaction. Herein, we show that this challenge can be addressed through the dynamic in-situ reconstruction of a CuO/In2O3 precursor under electrochemical CO2 reduction conditions. By employing in-situ electrochemical spectroscopy techniques in combination with theoretical calculations, we demonstrate that the presence of In2O3 facilitates the complete reduction of CuO to metallic Cu. This in-situ reconstruction produces electron-rich Cu-In2O3 interfaces, characterized by a reduced work function and an upshifted Cu 3d-band center, which promote CO2 activation and the formation of COOH/CO intermediates. Those interfacial properties lead to a pronounced electronic coupling that endows the electrocatalyst with high CO2-to-CO selectivity at low potentials. Specifically, the optimised Cu/In2O3 achieves CO Faradaic efficiency above 90% across-0.5 to-0.9 V vs. the reversible hydrogen electrode, reaching 97.6% at-0.6 V in a H-type cell, and sustains a high CO selectivity of 96.0% even at an ultralow potential of-0.2 V in a flow-cell configuration. These findings underscore the crucial role of electron-rich interfaces in directing CO2 reduction with exceptional selectivity and activity toward CO formation. (c) 2026, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Direct separation of xenon (Xe) and krypton (Kr) from air or spent nuclear fuel reprocessing off-gases is highly challenging due to their similar kinetic diameters. Herein, two three-dimensional porous organic polymers (POPch-SF and POP-ch-4F) were designed and synthesized by using thienothiophene and 1,2,4,5-tetrafluorobenzene as monomer, which was used to separate from Xe/Ke. POP-ch-SF exhibits high chemical stability, abundant micropores, and a microelectric field within its channels-enabled by the mixed linkers. The result found that POP-ch-SF have an Xe adsorption capacity of 2.04 mmol g- 1 and an IAST Xe/Kr selectivity of 11.8 at 298 K, outperforming most reported POPs. Breakthrough experiments yield an Xe/Kr selectivity of 9.96, demonstrating potential for practical industrial separation. DFT calculations confirm that the microelectric field, constructed by 1,2,4,5-tetrafluorobenzene and thienothiophene, enhances the interaction between the material and Xe.

The overuse of antibiotics poses severe threats to both the environment and public health. Complex coexisting ions and compounds in antibiotic-containing wastewater significantly impair the performance of the adsorbent used for pollutant removal. This study proposes a green activation strategy based on the longan seeds-H3BO3-KOH system, successfully synthesizing hierarchically porous biochar (P-BBC-2) with exceptional anti-ionic interference capability, which simultaneously integrates high adsorption performance, catalytic potential, and high yield. The maximum adsorption capacity of P-BBC-2 (1295.45 mg g(-1)) is significantly greater than traditional activation process (P-BBC-0, 1092.28 mg g(-1)) for adsorbing lomefloxacin (LOM), with a 12-fold increase over commercial activated carbon(100.49 mg g(-1)). More importantly, both in static adsorption and fixed-bed experiments conducted in complex multi-ion environments, P-BBC-2 demonstrates superior interference-resistant adsorption performance. The adsorption mechanism study reveals that the removal performance enhancement of P-BBC-2 stems from the synergistic effect of B2O3 templating and KOH channeling activation, which generates abundant micropores (1-2 nm) matching the size of LOM. Concurrently, its large mesoporous structure (pore size >10 nm) provides rapid mass transfer channels. While pi-pi interactions are pivotal physical interactions, with hydrogen bonding, electrostatic interactions, and Lewis acid-base interactions collectively contributing. In addition, P-BBC-2 can activate peroxymonosulfate (PMS) for LOM degradation. This multifunctional biochar integrates cost-effectiveness, high efficiency, and environmental adaptability, demonstrating comprehensive advantages from preparation to application. It provides theoretical and practical solutions for complex antibiotic wastewater treatment through its adsorption-degradation system.

The development of efficient, stable, and cost-effective bifunctional electrocatalysts for the hydrogen evolution reaction (HER) and the chlorine evolution reaction (CER) is critical for energy-saving chlor-alkali production and direct seawater...

Photocatalytic uranium extraction from seawater represents an attractive strategy for supporting the sustainable development of nuclear energy while addressing environmental concerns. Covalent organic frameworks (COFs) are emerging photocatalysts for uranium extraction, but further improvements in their synthesis, stability, and photoelectronic properties are required. Herein, a cyano-enhanced COF photocatalyst (COF-CN) was successfully synthesized via beta-ketoenamine linkage. The introduction of the cyano group as a strong electron acceptor improves photogenerated charge separation and coordination with uranyl ions, resulting in a 27.7% higher uranium extraction rate than its non-cyano counterpart. Benefiting from its outstanding photocatalysis, high selectivity, and antibacterial properties, COF-CN achieves a uranium extraction capacity of 11.5 mg/g in natural seawater over a one-week assay (12 h visible light/12 h dark cycle) without sacrificial agents, surpassing some currently reported photocatalysts. Moreover, the final photocatalytic product is identified as a highly stable uranium crystalline compound ((UO2)O2 & sdot;2H2O), which can be readily recycled without secondary environmental risks. This study presents a strategy that expands the rational design of COF-based photocatalysts, offering new insights for developing the ocean as a sustainable nuclear fuel source.

The selective separation of hydrogen isotopes under mild cryogenic conditions remains a formidable challenge due to their nearly identical physicochemical properties. Here, we report a dual strategy of pore topology design and paired Cu(II) open metal sites (OMS) synergistic engineering to amplify chemical affinity quantum sieving (CAQS). Among three tailored Cu(II)-MOFs, Cu-ATC exhibited exceptional performance, achieving a D2/H2 selectivity of 20 at 50 K (10 mbar) and 1.8 in breakthrough experiments at 77 K, demonstrating excellent H2/D2 separation performance. The ultramicroporous topology of Cu-ATC fixes a Cu···Cu distance of 5.98 Å within one-dimensional channels, while Jahn-Teller distortion induces axial elongation at each Cu(II) center, thereby enhancing the accessibility of the dz2 orbitals for interaction with hydrogen isotope molecules. This structural combination creates two closely spaced OMSs that enhance differential interactions with H2 and D2, thereby driving isotope separation via CAQS. The distinct binding strength is evidenced by in situ DRIFTS (v(H-H)/ v(D-D) red-shift of 203 cm-1/ 147 cm-1) and by DFT calculations showing stronger adsorption of H2 ( - 9.7 kJ mol-1) and D2 ( - 13.0 kJ mol-1). These microscopic differences account for the observed D2/H2 selectivity, highlighting the potential of paired OMSs engineering for CAQS-based isotope separation under mild cryogenic conditions.

Since red light occupies > 40% of visible sunlight, developing materials that absorb red light is crucial. Herein, two imine-linked Covalent Organic Frameworks(COFs) with different numbers of benzene rings, namely PorBPDA-COF and Por-TPDA-COF, were synthesized from 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin reacted with 4,4'-biphenyldicarboxaldehyde and 4,4"-p-terphenyldicarboxaldehyde, respectively. The integration between the electron-rich porphyrin donors and biphenyl and terphenyl acceptors into D-A structure resulted in reduced bandgaps for both COFs. The UV-vis spectroscopy indicated that Por-BPDA-COF and Por-TPDA-COF can absorb red light due to low band gaps, and thus were used for the reduction of U(VI) under red light. The effects of different conditions were examined on the photocatalytic reduction of U(VI) by Por-BPDA-COF and Por-TPDACOF. The results showed that the removal rates of Por-BPDA-COF and Por-TPDA-COF under the optimal conditions(ascorbic acid as the sacrificial agent, pH = 3, U(VI) = 57.5 ppm) were 88.9% and 77.6%. The higher efficiency of Por-BPDA-COF was due to stronger D-A structure and larger planarity than Por-TPDA-COF. Combined with XPS and EPR characterizations, the mechanism was that U(VI) was reduced to UO2 & sdot;nH2O. In addition, the U(VI) removal efficiency by Por-BPDA-COF(89%) remained unaffected by the competing ions. Compared with the narrow-spectrum absorption materials, Por-BPDA-COF exhibited excellent advantage(84.5%) on the removal of U(VI) from moderately acidic solution (pH = 3) under sunlight because of the wide-spectrum absorption covering the red light. This research provides valuable insights for expanding the light absorption range of photocatalysts to increase the utilization of sunlight and reveals that more planar structure is more favorable for charge transfer.

The development of efficient and stable oxygen evolution reaction (OER) electrocatalysts for seawater electrolysis is vital to enable sustainable hydrogen production in coastal and arid regions without further burdening scarce freshwater resources. Here, we report the design of an iron-modified cobalt-chromium layered double hydroxide (Fe-CoCr LDH) derived from a cobalt-based metal-organic framework (Co MOF) for the OER in alkaline seawater media. The synthesis was carried out entirely at room temperature using a rapid, solution-based process. The resulting Fe-CoCr LDH catalyst demonstrates high OER activity, achieving low overpotentials of 250, 300, and 320 mV at current densities of 100, 500, and 1000 mA cm-2, respectively. Furthermore, the catalyst exhibits very good long-term stability in both 1 M KOH and 6 M KOH natural seawater, maintaining performance over 100 hours at 100 and 500 mA cm-2. These results highlight the potential of earth-abundant transition metal-based LDHs as efficient OER electrocatalysts for seawater electrolysis applications.

As a novel organic semiconductor derived from biomass, hydrothermal carbonation carbon (HTCC) usually exhibits an amorphous structure due to its well-recognized formation pathway based on 5-hydroxymethylfurfural (HMF), which impedes charge transfer and consequently restricts the photocatalytic activity. Herein, we report a crystalline HTCC photocatalyst produced via an unusual synthesis route applied to cellulose in the presence of an oxidant. Notably, the crystalline structure of cellulose was retained and became highly aromatized during the process, leading to significantly enhanced charge transfer efficiency and an increased density of active sites. Moreover, unlike other reported HTCC photocatalysis, the highly active hydrogen radicals (H•) were identified as the dominant active species governing photocatalytic Cr(VI) reduction over crystalline HTCC. As a result, this crystalline HTCC exhibited dramatically enhanced photocatalytic removal efficiencies of Cr(VI) and microcystin-LR (MC-LR) due to the highly efficient charge transfer, abundant active sites as well as highly active hydrogen radicals.

NiFe layered double hydroxide (NiFe LDH) has emerged as a promising catalyst for the oxygen evolution reaction (OER); however, its hydrogen evolution reaction (HER) activity remains suboptimal due to unfavorable electronic structures, particularly the d-electron density of metal sites, which impede water dissociation and lead to poor hydrogen adsorption/desorption capabilities. Herein, we introduce an efficient cooperative d-electron density regulation (CDDR) engineering to comprehensively optimize the delectron density of NiFe LDH by grafting MoOx-modified NiFe LDH nanosheets onto porous nickel particles (PNPs). The PNPs facilitate d-electron density modulation along the edges of the nanosheets, while the MoOx species enable d-electron density modulation across the plane of the nanosheets, thus cooperatively constructing enriched d-electron density in NiFe LDH. Theoretical studies validate the CDDR process and reveal that the enriched d-electron density accelerates water dissociation and optimizes the hydrogen adsorption behavior of NiFe LDH. Asa result, the engineered catalyst exhibits significantly improved HER activity, achieving an ultra-low overpotential of 38 mV at 10 mA cm-2 in 1 M KOH. Additionally, the CDDR-optimized catalyst also exhibits good OER performance, demonstrating excellent bifunctional performance for overall water splitting in both alkaline freshwater and seawater electrolytes. This work presents a novel CDDR strategy for engineering NiFe LDH into efficient HER catalysts without compromising its OER activity, potentially paving the way for the development of active and robust electrocatalysts for sustainable energy applications. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

In this study, a high-performance bifunctional benzoxazine monomer (designated as TDT-fa) was successfully synthesized via a two-step approach using eugenol, furfurylamine, paraformaldehyde, and 1,1,5,5-tetramethyl3,3-diphenyl trisiloxane as raw materials. The chemical structure of the product was comprehensively characterized by nuclear magnetic resonance spectroscopy (1H NMR and 13C NMR) and Fourier transform infrared spectroscopy (FT-IR), confirming the successful synthesis of the target molecule. The curing kinetics behavior of TDT-fa was deeply studied by differential scanning calorimetry (DSC). The apparent activation energies of its curing reaction were calculated using the Kissinger method and the Ozawa method, with the values being 100.60 kJ/mol and 112.22 kJ/mol respectively. The two values were close. Further analysis was conducted using the Starink method, and the average apparent activation energy of the curing reaction was finally determined to be 111.14 kJ/mol. It was also confirmed that the reaction mechanism of this curing reaction conforms to the characteristics of autocatalytic reaction. The results of thermogravimetric analysis (TGA and DTG) show that the residual carbon rate (Yc) of TDT-fa at 800 degrees C in a nitrogen atmosphere is as high as 50.41%, indicating that this resin has excellent thermal stability. Furthermore, the solidified TDT-fa resin exhibits unique reprocessability. Under specific conditions, it can achieve nearly 100% reprocessability. This characteristic effectively addresses the environmental pollution problem caused by traditional benzene pyrazine resins after use, providing an important basis for its application in the field of high-performance and environmentally friendly materials.

A bio-based benzoxazine monomer was synthesized from renewable equol, furfurylamine, and paraformaldehyde via a Mannich condensation. The chemical structure was confirmed by 1H and 13C NMR, Fourier transform infrared spectroscopy (FT-IR), and high-resolution mass spectrometry (HR-MS). The polymerization behavior of the resin was investigated by differential scanning calorimetry (DSC) and in situ Fourier transform infrared spectroscopy. Thermogravimetric analysis (TGA) and micro-scale combustion calorimetry (MCC) were employed to evaluate thermal stability and flammability. The resulting bio-thermoset exhibits a high char-forming tendency and low flammability, with Td10 at 427℃, Tg at 238℃, heat-release capacity (HRC) of 64 J·g⁻¹·K⁻¹, and total heat release (THR) of 10.5 kJ·g⁻¹. This work provides a facile and route to a novel bio-based benzoxazine from renewable building blocks that combines excellent processability with superior thermal and flame-retardant performance, offering significant promise for high-performance fire-safe materials.

Confining active nanoparticles within specific nanoscale spaces is a promising strategy to improve the catalytic activity, selectivity and stability of catalysts. In this study, we present a lattice-matching approach to confine Co particles within ZnO layers (ZnO/Co/ZnO) for CO2 hydrogenation, a critical and challenging reaction in the field of CO2 utilization and energy production. XRD patterns reveal that the lattice mismatch between ZnO and hexagonal wurtzite CoO (w-CoO) is only 0.18%, facilitating the epitaxial growth of w-CoO on the ZnO surface, or vice versa. This minimal mismatch enables the successful confinement of w-CoO within the ZnO interlayers. This advanced methodology can also be adapted to diverse ZnO morphologies, allowing the optimization of the confined catalyst microstructure. Significantly, when Co particles are confined within the interlayer of ZnO, they exhibit excellent catalytic activity, achieving a rate of 15.8 μ molCO2⋅gCo−1⋅s−1 for CO2 hydrogenation reaction. Moreover, no appreciable deactivation was observed even after 700 h of continuous operation. These results introduce a novel approach for the development of confined catalysts with enhanced activity and long-term stability.

The addition of Ce to V-Ti based catalysts is a promising way to improve the middle and low temperature activity for selective catalytic reduction of NO with NH3 (NH3-SCR). In this study, a series of V-Ce loaded TiO2 catalysts were prepared by impregnation method and studied by in situ spectroscopy experiments and ex situ characterizations. Results show that the SCR reaction on the surface of V-Ce/TiO2 catalysts obeys the Eley-Rideal mechanism. The presence of Ce in V-Ce/TiO2 catalysts strengthens the NH3 adsorption energy of V and promotes its rupture of N-H bond, thus facilitating the reactions, with 100 % NO conversion and 100 % N2 selectivity obtained at 250 degrees C over 2V-10Ce/Ti. During the reaction, the Ce4+ ions are reduced by NH3 + NO to yield N2 and Ce3+ ions (the reduction half cycle), which will then be re-oxidized to Ce4+ ions by O2 (the oxidation half cycle), thereby ensuring the proceeding of the overall reaction.

In the pursuit of sustainable carbon dioxide (CO2) reduction strategies, this study explores the potential of a novel dual piezoelectric system comprising K0.5Na0.5NbO3 (KNN) and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) for enhanced CO2 catalytic reduction. The dual piezoelectric coating fabricated using a simple and adjustable method demonstrated remarkable versatility in applications to diverse surfaces and shapes. This system not only amplifies piezoelectric carrier generation but also enhances carrier separation and transfer through the synergistic effect of the dual piezoelectric materials. The integration of acetylene black further improves the conductivity and optimizes the piezoelectric catalytic performance. Under optimal conditions, the composite film achieves a significant carbon monoxide (CO) yield of 191.6 mu mol g-1 h-1, representing a 13-fold enhancement over pure KNN. In addition, we investigated the underlying piezoelectric catalytic mechanism, revealing the critical role of the band structure and polarization fields in facilitating CO2 reduction. This work not only underscores the effectiveness of the dual piezoelectric system but also paves the way for the development of high-performance piezoelectric catalysts with broad industrial applications, advancing the field of piezoelectric catalysis for more sustainable CO2 reduction technologies.