Fluorine-containing silicon slag will lead to environmental pollution and resource waste. The effective utilization of silicon slag faces significant challenges. The synthesis of molecular sieves from silicon slag represents a promising approach for the high-value conversion of this solid waste. In this study, fluorine-containing silicon slag was converted into ZSM-5 molecular sieve through a simple treatment method. The effects of pH, temperature, silicon-to-aluminum ratio, and crystallization time on the synthesis of mesoporous ZSM-5 were investigated. The catalyst [C12Py]3(NH4)3Mo7O24/ZSM-5 was synthesized by loading [C12Py]3(NH4)3Mo7O24 onto the synthesized ZSM-5. The [C12Py]3(NH4)3Mo7O24/ZSM-5 catalyst can remove 99.5% of dibenzothiophene (DBT) in one hour under optimal conditions. The oxidative desulfurization efficiency can still reach 92.1% after 9 cycles. The synthesized ZSM-5 and catalyst were characterized by XRD, FT-IR, XPS, SEM, TEM, XRF, EPR, and other methods. The electron transfer between ZSM-5 and [C12Py]3(NH4)3Mo7O24 results in the generation of electron-rich Mo species, enhancing the catalytic efficiency. Finally, the reaction mechanism was proposed through XPS, EPR, and free radical quenching experiments. This work presents a new method for utilizing fluorine-containing silicon slag to synthesize high value products and its application in oxidative desulfurization of dibenzothiophene.

In recent years, the regulatory mechanism of oxygen vacancies on oxidation desulfurization performance has gradually become a research hotspot. This work focused on the synthesis of an oxygen vacancy-rich MoO3/CeO2 catalyst. This catalyst was prepared by uniformly loading active species onto a cerium oxide (CeO2) support via a CTAB-assisted reverse microemulsion method. Comprehensive characterization techniques and density functional theory (DFT) calculations confirm that oxygen vacancies enhance the metal-support interaction. This promotes electron transfer from the support to molybdenum (Mo), converting Mo into electron-rich active sites, which in turn facilitates the conversion of H2O2 into hydroxyl radicals (•OH), hence playing a pivotal role in subsequent oxidation desulfurization (ODS) processes. ODS experiments demonstrated that the 25% MoO3/CeO2-350-2 catalyst exhibits outstanding catalytic activity, achieving complete desulfurization of dibenzothiophene (DBT) within 35 min under optimal conditions. It also displayed excellent desulfurization efficiency for other thiophene-derived sulfides. Moreover, it maintained a high conversion efficiency of 90.63% even after 9 cycles, indicating the outstanding stability of the catalyst. This work provides new insights for designing efficient oxygen vacancy-rich catalysts.

Addressing the inherent activity and stability limitations of RuO2 catalyst in water electrolysis, this study introduces a targeted electronic structure modulation approach through the simultaneous incorporation of functionally complementary Mo (cation) and S (anion) heteroatoms. This dual-site synergistic doping strategy precisely regulates both the Ru d-band center and the O p-band center within RuO2, optimizing the coupling strength and energetic alignment of the d-p orbitals. Therefore, the Mo, S-doped RuO2 nanofibers (NFs) balance the adsorption/desorption energetics of intermediates and accelerates reaction kinetics. This new structure also benefits to enhance the durability. Consequently, the resulting Mo, S-doped RuO2 NFs deliver superior bifunctional water splitting performance, requiring only 221.0 mV overpotential for oxygen evolution reaction at 10 mA cm−2 and maintaining the performance up to 200 h at 1 A cm−2, while achieving hydrogen evolution reaction to feature mere 187.7 mV overpotential at 1 A cm−2 and 200 h stability at this current density. This work unlocks a new pathway to promote the electrocatalytic performance of Ru-based catalysts via d-p band center engineering under industrial-level water electrolysis conditions.

Fe/Ni incorporation modulates W 18 O 49 electronic structure and oxygen vacancy concentration to produce abundant active sites. The optimized catalyst delivers excellent mild-condition deep desulfurization efficiency and cycling stability.

Owing to their quantum confinement, quantum dots (QDs) can efficiently generate singlet oxygen, a highly reactive oxygen species (ROS). Although promising for photocatalytic water remediation, their practical application remains limited. Their nanoscale dimensions render them more challenging to deploy than bulk heterogeneous photocatalysts; specifically, their separation and recycling are complex, and catalyst leaching poses a significant issue. In this study, we evaluated several chemical immobilization methods initiated by cold plasma discharge (CPD) to fabricate supported QD-based catalysts for the photodegradation of organic pollutants. Using CdS QDs as a model system, we probed their capacity to generate singlet oxygen. The resin substrates were fabricated by LCD 3D printing and microtextured with fractal architectures. Among the different immobilization strategies, the most successful employed a secondary nanostructured ZnO support to enforce a monolayer dispersion of the QDs. Subsequent in situ encapsulation by a metal–organic framework (MOF) further improved the photostability of the catalyst. This study provides valuable insights and new directions for the facile surface immobilization of functional QDs within controlled architectures for the efficient remediation of organic-contaminated water.

Conjugated polymers featuring donor–acceptor (D-A) architectures have emerged as promising candidates for visible-light-driven hydrogen evolution, owing to their tunable optoelectronic properties. However, achieving high photocatalytic activity without noble-metal cocatalysts remains challenging. Herein, we report a series of D-A type conjugated polymers based on dibenzothiophene sulfone (BTDO) as an electron acceptor and 3,4-ethylenedioxythiophene (EDOT) as an electron donor, synthesized via Suzuki polycondensation. By optimizing the donor/acceptor feed ratio, the optimal copolymer, EDOT-BTDO-5, delivers a hydrogen evolution rate (HER) as high as 87.5 mmol h−1 g−1 was achieved under visible-light irradiation (λ > 420 nm) without any Pt cocatalyst. To further boost the charge separation efficiency, a thiophene π-bridge was introduced, yielding a D-A-π-A ternary copolymer, EDOT-BTDO-T, which exhibits a significantly enhanced HER of 103.45 mmol h−1 g−1, along with remarkable operational stability, retaining ~69% of its initial activity after 20 h of continuous illumination. Comprehensive characterization, including photoelectrochemical analysis and density functional theory (DFT) calculations, reveals that the incorporation of EDOT broadens the visible-light absorption range, while the thiophene π-bridge extends π-conjugation, and facilitates efficiency. This work demonstrates a molecular engineering strategy to construct high-performance, metal-free organic photocatalysts by tailoring D-A and D-A-π-A architectures, providing valuable insights for sustainable photochemical energy conversion.

A bimetallic CoMnOx catalyst supported on carbon nanofibers has been constructed for peroxymonosulfate (PMS) activation.

The growing demand for sustainable energy solutions has prompted significant interest in photocatalytic hydrogen production as a promising alternative to fossil fuels. Covalent organic frameworks (COFs), known for their crystalline porosity, tunable structures, and pi-conjugated networks, have emerged as ideal candidates for photocatalysis. However, their limited charge separation efficiency and poor hydrophilicity hinder their full potential. This study introduces a novel ternary composite system, Ti3C2(10)@In2O3(50)@COF-3, which effectively combines the advantages of COFs, In2O3, and Ti3C2 to overcome these limitations. By leveraging the conductive properties of Ti3C2, the active centers of In2O3, and the porous nature of COFs, the composite achieves a remarkable hydrogen evolution rate of 12901.23 mu mol g-1 h-1, a 14-fold increase over pure COF-3. Comprehensive structural characterizations, including PXRD, FT-IR, BET surface area measurements, and XPS, confirm the successful integration of these components and demonstrate the structural stability of the composites. The enhanced photocatalytic activity is attributed to the synergistic effects of efficient charge separation, rapid electron transport through the Ti3C2 network, and improved hydrophilicity, which together promote superior photocatalytic performance. AQE values further confirm the composites' enhanced light absorption capacity. The photocatalytic mechanism is elucidated through electrochemical impedance spectroscopy, transient photocurrent responses, and photoluminescence measurements, revealing the critical role of Ti3C2 as an electron transfer conduit. This study not only highlights the successful design of multifunctional hybrid photocatalysts but also provides a promising strategy for developing highly efficient, stable, and scalable photocatalysts for sustainable hydrogen production.

Extending the oligothiophene linkers (T → DT → TT) in the D–A polymer TPA-BTDO enhances H 2 evolution by improving coplanarity and reducing charge recombination, with TPA-TT-BTDO achieving HER rates of 101.2 (visible) and 125 mmol h −1 g −1 (sunlight).

The massive emission of CO2 poses a huge challenge to global environmental protection. Both oxygen vacancies (OVs) and hydrogen spillover effect are critical to CO2 hydrogenation, but their synergistic mechanism over transition metal alloys remains insufficiently explored. In this work, a facile one-pot liquid-phase reduction method for synthesizing Fe-Co alloy catalysts with tunable Fe/Co ratios (7:1-1:13) without pre-activation, avoiding rare metals to realize cost advantage. The physico-chemical properties of catalysts were systematically characterized by XRD, XPS, SEM/TEM, BET, EPR, H-2-TPR, CO2-TPD, in-situ DRIFTS. It was found that Fe incorporation promotes OV formation by inducing surface oxidation, while Co enrichment enhances hydrogen spillover via increased exposed metallic Co sites. The optimal Fe1Co9 catalyst exhibits superior performance: >99% CH4 selectivity, and a CH4 space-time yield of 57.9 mmolg(cat)(-1)h(-1) at 280 degrees C and 6.0 MPa, meanwhile Fe1Co9 favors the direct *CO-mediated pathway (CO2 -> *CO -> *CH -> CH4) instead of the formate pathway, with *CO as the key intermediate. DFT calculations further confirm that Fe1Co9 has a CO2 adsorption energy of 1.68 eV, and a low Gibbs free energy difference (Delta G) of 0.95 eV for the rate-limiting step (*CH -> *CH2). This work innovatively realizes the synergistic regulation of OVs and hydrogen spillover via Fe/Co ratio tuning, providing a new strategy for constructing low-cost, high-performance transition metal alloy catalysts.

Conjugated polymer photocatalysts with donor-acceptor (D-A) structures have shown great potential in the field of photocatalysis and have attracted considerable research interest in recent years. However, the rational design of highly efficient organic photocatalysts for hydrogen evolution remains a significant challenge. In this work, a series of D-pi-A conjugated polymer photocatalysts with tunable compositions were synthesized via Suzuki coupling, employing thieno[3,2-b]thiophene as the electron donor and dibenzothiophene sulfone as the electron acceptor. By precisely controlling the feed ratio, the optimized copolymer, designated as TTTDBSO-7, achieved a donor-to-acceptor molar ratio of 1:7 and incorporated 7 wt% of a bridging agent. Remarkably, without the assistance of any noble-metal cocatalyst (e.g., platinum), TTTDBSO-7 exhibited an impressive hydrogen evolution rate (HER) of 68.52mmol h(-1) g(-1) under visible-light irradiation (lambda > 420 nm), representing a 264.56% enhancement compared to the benchmark poly(dibenzothiophene sulfone) (PDBTSO), which displayed an HER of 18.78mmol h(-1) g(-1). Comprehensive physicochemical characterizations and photoelectrochemical analyses confirmed that TTTDBSO-7 possesses superior visible-light absorption, enhanced charge separation efficiency, and improved transport of photoexcited carriers. These experimental observations were further supported by density functional theory (DFT) calculations. This study provides valuable insights into the molecular engineering of conjugated organic polymer photocatalysts and offers a promising strategy for the development of efficient metal-free materials for solar-driven hydrogen production.

Abstract The rational design of catalyst supports to achieve optimal metal-support interaction is critical for advancing Pd-based electrocatalysts for formic acid oxidation. Herein, we reported a thermally driven strategy to modulate the chemical state of sulfur on carbon support derived from propanethiol-functionalized carbon, which enabled bidirectional tuning of the Pd state and fundamentally altered the reaction pathway of formic acid oxidation. With an optimized calcination temperature of 700 °C, the Pd/SC-700 catalyst, featuring an exclusive thiophenic sulfur configuration, exhibited the strongest metal-support interaction, delivering an exceptional mass activity of 2222 mA mg–1 (8.3 times that of Pd/C), considerably superior stability (14 times that of Pd/C), and faster charge-transfer kinetics for formic acid oxidation. Gas chromatography analysis revealed a marked shift in reaction selectivity. Although CO remained the dominant product, its fraction dropped from 95.4% on Pd/C to 73.2% on Pd/SC-700, while the emergence of 7.2% CO2 directly confirmed activation of the direct dehydrogenation pathway. Kinetic analysis showed a linear j–v0.5 relationship (j = 0.62 + 0.204v0.5), indicating diffusion-controlled behavior with enhanced mass transport. This work provides a new strategy of thiol modification followed by thermal treatment that offers a simple yet scalable route to synthesize high-performance anode electrocatalysts for direct formic acid fuel cells.

Ultra-deep desulfurization of fuels is critical for environmental protection and clean energy supply. Oxidative desulfurization (ODS) is a promising approach due to moderate operating conditions and excellent efficiency toward aromatic sulfur-containing molecules. Herein, a novel Zr-doped W18O49 supported on halloysite nanotube (HNT) composite catalyst (Zr-W18O49/HNT) was fabricatedvia a solvothermal method. Characterizations (XRD, FT-IR, XPS, EPR, etc.) confirmed the doping of Zr into the W18O49 lattice and the formation of abundant oxygen vacancies. Meanwhile, HNT suppresses aggregation and exposes more active sites on the surface. The optimized Zr0.6-W18O49/HNT catalyst achieves complete removal of dibenzothiophene (DBT) in 20 min under moderate conditions (60 °C, O/S = 3) and retains 87.5% removal efficiency after 8 cycles. Quenching experiments and EPR revealed that hydroxyl radicals (•OH) are the dominant reactive species. Density functional theory (DFT) calculations further demonstrated that Zr doping enhanced H2O2 adsorption and activation on the catalysts’ surface, thereby promoting the generation of •OH. This work provides a feasible modification strategy for designing high-efficiency supported catalysts for industrial ODS applications.

The efficacy of RuO2 as a bifunctional electrocatalyst for alkaline water electrolysis is usually constrained by its sluggish hydrogen evolution kinetics and poor stability. Herein, we report the fabrication of ternary RuCoMoO x nanofibers (NFs) incorporating oxide heterojunctions, which address these issues through interfacial charge engineering. The electron redistribution induced by the constructed interface optimizes the local electronic environment, endowing the catalyst with superior activity and stability for both the hydrogen and oxygen evolution reactions (HER/OER). The RuCoMoO x NFs require ultralow overpotentials of 274.8 mV for the HER and 367.9 mV for the OER to deliver a high current density of 1 A cm-2, surpassing commercial Pt/C and RuO2 benchmarks. Moreover, the catalyst possesses superior operational stability for both the HER and the OER at 1 A cm-2 compared to Pt/C and RuO2, respectively. In a practical electrolyzer, the assembled symmetric RuCoMoO x NFs‖RuCoMoO x NFs system delivers a much lower working voltage than Pt/C‖RuO2 and maintains stable operation at 1 A cm-2 for 60 h. This work validates interfacial charge engineering as a key strategy for creating high-performance noble-metal-lean electrocatalysts for industrial water electrolysis.

Oxidative desulfurization (ODS) is a crucial technology for producing clean, sulfur-free fuels. Molybdenum-based catalysts face the challenges of easy shielding of active metal centers and low utilization of active sites. Here, Nrich ligand-anchored mesoporous (9.45 nm) Mo single-atom active sites catalysts were constructed based on the strategy of ZIF-8 via spatial domain restriction using melamine as a pyrolytic agent. Through aberration-corrected HAADF-STEM, XANES, EXAFS and other characterization, Mo atoms were confirmed to be well-dispersed on N-doped carbon matrix. The ODS experiments demonstrated that the catalyst displayed excellent catalytic activity, achieving complete DBT conversion in 30 min under optimal conditions, with a turnover frequency (TOF) number reaching 72.87 h-1, surpassing most previously reported Mo-based catalysts. Experimental results and computational calculations suggest the dominant role of single-atom MoN3 sites in activating H2O2 to produce center dot OH and center dot O2-. The uniformly distributed MoNx part uses the N coordination number to modulate the electronic structure and geometric configuration to promote electron transfer and stabilize the mesoporous structure enhancing the mass transfer of target pollutants. This study elucidates the structure-activity relationship between the coordination microenvironment of active metal centers and ODS performance, offering new insights for the design of highly active Mo-based catalysts.

Hydrazine oxidation‐assisted water electrolysis emerges as a promising strategy with low thermodynamic requirements and eco‐friendly byproducts, yet designing highly efficient bifunctional catalysts for alkaline hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) remains challenging. Herein, a novel heterostructure comprising low‐crystallinity Ruthenium molybdenum (RuMo) alloy nanofibers coupled with molybdenum dioxide (MoO 2 ) domains is presented as a bifunctional electrocatalyst for both HER and HzOR. The optimized catalyst achieves ultralow overpotentials of 31/170 mV for HER at 10/1000 mA cm −2 and working potentials of –0.073/0.028 V for HzOR at 10/500 mA cm −2 , significantly surpassing the benchmark Pt/C catalyst. Theoretical calculations reveal that the coupling of RuMo alloy with MoO 2 regulates the d ‐band center, promotes water dissociation and modulates H* adsorption, thereby realizing superior HER kinetics. The heterostructure also optimizes the reaction pathway to reduce the energy barrier for hydrazine dehydrogenation, achieving an enhanced HzOR performance. Inspiringly, the assembled two‐electrode system for overall hydrazine splitting (OHzS) achieves a low power consumption of 1.52 kWh m −3 H 2 , greatly surpassing Ru NFs‐based cell (3.78 kWh m −3 H 2 ). Furthermore, a rechargeable zinc (Zn)‐hydrazine battery is constructed, showing great potential in practical application.

Hydrazine oxidation-assisted water electrolysis emerges as a promising strategy with low thermodynamic requirements and eco-friendly byproducts, yet designing highly efficient bifunctional catalysts for alkaline hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) remains challenging. Herein, a novel heterostructure comprising low-crystallinity Ruthenium molybdenum (RuMo) alloy nanofibers coupled with molybdenum dioxide (MoO2) domains is presented as a bifunctional electrocatalyst for both HER and HzOR. The optimized catalyst achieves ultralow overpotentials of 31/170 mV for HER at 10/1000 mA cm-2 and working potentials of -0.073/0.028 V for HzOR at 10/500 mA cm-2, significantly surpassing the benchmark Pt/C catalyst. Theoretical calculations reveal that the coupling of RuMo alloy with MoO2 regulates the d-band center, promotes water dissociation and modulates H* adsorption, thereby realizing superior HER kinetics. The heterostructure also optimizes the reaction pathway to reduce the energy barrier for hydrazine dehydrogenation, achieving an enhanced HzOR performance. Inspiringly, the assembled two-electrode system for overall hydrazine splitting (OHzS) achieves a low power consumption of 1.52 kWh m-3 H2, greatly surpassing Ru NFs-based cell (3.78 kWh m-3 H2). Furthermore, a rechargeable zinc (Zn)-hydrazine battery is constructed, showing great potential in practical application.

Efficient photocatalysts rely on constructing heterostructure with reasonable configuration. In this study, a novel conjugated polymer with a D-pi-A structure was fabricated from polycondensation of perylene diimide and dibenzothiophene sulfone through the suzuki coupling reaction, during which the biphenyl was incorporated as a it-bridge. The photocatalytic hydrogen evolution performance of these copolymers were optimized by introducing different mass fractions of it-bridges via adjusting the additions of biphenyls The optimized PyBpDBSO-5 copolymer, with 17 wt.% perylene diimide and 5 wt% biphenyl, obtained photocatalytic hydrogen productivity of 48.54mmol/h g- 1 under visible light without adding Pt as cocatalyst, which is 146.1 % improvement compared to the poly(dibenzothiophene-S,S-dioxide) (PDBTSO, 19.72mmol/h g- 1). Based on the analysis of physical and chemical properties, electrochemical testing, the significant advantages of D-pi-A configuration in promoting light absorption, photogenerated carriers transfer and separation was confirmed, which was further rationalized by the larger co-planarity of the polymer based on DFT calculations. This study provides inspiration about construction of conjugated organic polymer catalyst towards efficient photocatalysts.

Oxidative desulfurization (ODS) is an effective technology to eliminate sulfur compounds from fuels. Zr-based MOFs are frequently employed as ODS catalyst support. In this paper, a Zr-based MOF (NNU-28) catalyst was synthesized by a hydrothermal method, and three hydrophobic catalysts (OTES-NNU-28, DTS-NNU-28, HDTMSNNU-28) were synthesized by surface modification with organosilanes of different alkane chains. Then the hydrophobic OTES-NNU-28, DTS-NNU-28, and HDTMS-NNU-28 were used as ODS catalysts directly without the loading of active components. The catalysts before and after hydrophobic modification were characterized by FTIR, XPS, XRD, FE-SEM, TEM, Contact angle test, UV-Vis DRS, Mott-Schottky and N2 adsorption-desorption. Under appropriate reaction circumstances, OTES-NNU-28 can completely remove DBT in 50 min and has a good removal efficiency for BT, 4,6-DMDBT, and DBT. The removal efficiency for DBT could reach 85% after 12 cycles. We found that the electronic structure of NNU-28 is more favorable for charge migration due to its anthracenebased ligand structure with a narrow band gap and higher electron density than other typical Zr-based MOFs, and the surface hydrophobicity modification greatly improves the ODS reaction rate and the stability of the catalyst, which also verifies that the degree of hydrophobicity modification needs to be in an appropriate range. Finally, the oxidation mechanism of the catalyst in the ODS process was examined.

In order to further boost the electrocatalytic performances of small organic molecule oxidation and maintain the structure stability of Pd-based catalyst during long cycle, a new ligand compound (i.e. propanethiol) was introduced into the Pd/C anode catalyst to prepared Pd/C-SH catalyst by two main steps of propanethiol adsorbed on Vulcan XC-72 carbon (C-SH) by water bath impregnation method and Pd nanoparticles anchored on the functionalized C-SH support by improved liquid reduction method. Results showed that the Pd nanoparticles with high dispersion in Pd/C-SH catalyst were obtained and their particle size distribution was in the range of 1.6-4.8nm. Moreover, Pd particle size became smaller with the modification of propanethiol, indicating that propanethiol could facilitate the formation of smaller Pd. Electrochemical measurements showed that the mass activity of Pd/C-SH (1229mAmg-1) was 4.6 times that of Pd/C (267mAmg-1) towards formic acid oxidation. Higher stability (30 times higher than Pd/C) and more faster charge transfer kinetics of oxidation reaction were also recorded for Pd/C-SH catalyst. The enhancement of electrochemical performances of Pd/C-SH catalyst might be related to highly dispersed Pd with reduced particle size, adjusted electronic structure of Pd as well as maintained stable Pd structure and particle size.