Search Results (172)

Ammonia decomposition over non-precious metal thermos-catalysts offers a viable and cost-effective pathway for sustainable hydrogen production. In this study, LaCeO₃ perovskite was synthesized using a citric acid complexation method and employed as a support for mono- and bimetallic catalysts prepared by incipient wetness impregnation, maintaining a total metal loading of 10 wt%. Structural and surface properties were systematically investigated using BET, XRD, H₂-TPR, SEM, TEM, and CO₂-TPD. Among the monometallic catalysts (Ni, Co, and Fe), 10%Ni/LaCeO₃ exhibited the highest activity, which is attributed to its enhanced reducibility and optimal surface basicity, facilitating NH₃ activation. Bimetallic systems (Ni-Co, Ni-Fe, and Co-Fe) with equal metal loadings (5 wt% each) showed better activity compared to their monometallic counterparts following the order: 5%Ni–5%Co/LaCeO₃ > 5%Ni–5%Fe/LaCeO₃ > 5%Co–5%Fe/LaCeO₃. The improved performance of the Ni-Co system is due to structural interactions between Ni and Co, which promote hydrogen desorption and accelerate N–H bond cleavage, while suppressing nitrogen recombination as the rate-limiting step. Further systematic optimization of the Ni/Co ratio showed that 8%Ni–2%Co/LaCeO₃ had the highest catalytic activity with consistent performance over 50 h. This optimal composition provides a balanced distribution of active metallic sites and moderate-to-strong basic sites, enhancing NH₃ adsorption and intermediate transformation. These findings show that LaCeO₃-supported Ni-Co catalysts are promising candidates for efficient hydrogen production from ammonia without using noble metals. Full article

The selective hydrogenation of p-chloronitrobenzene (p-CNB) to p-chloroaniline (p-CAN) is of great importance for the production of dyes, pesticides, and pharmaceuticals, but it is often plagued by the undesired hydrodechlorination side reaction. In this work, we report a PtNi bimetallic catalyst supported on nano-sized LTL zeolite (PtNi/Nano-HL) for the selective hydrogenation of p-chloronitrobenzene under mild conditions. The catalyst was systematically characterized by X-ray diffraction (XRD), nitrogen sorption (N₂ sorption), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and ammonia temperature-programmed desorption (NH₃-TPD). The results reveal abundant oxygen vacancies (RIR = 0.73) and an optimized distribution of medium–strong acid sites on the catalyst surface, as well as electronic interaction between Pt and Ni, which collectively enhance the catalytic performance. Remarkably, the PtNi/Nano-HL catalyst achieves 100% conversion and over 99% selectivity for p-chloroaniline under ambient conditions (30 °C, 0.1 MPa H₂) using ethanol as a solvent. Even after 24 recycling runs, it retains 100% conversion and >93% selectivity, demonstrating excellent stability. Moreover, the catalyst requires an extremely low Pt loading (only 0.11 wt%) and exhibits good substrate universality for various substituted nitroarenes. This work provides a promising strategy for designing high-performance bimetallic catalysts on nano-zeolite supports for the selective hydrogenation of halonitrobenzenes. Full article

The selective conversion of high-molecular-weight paraffins (C₂₀–C₄₀) into linear alpha-olefins is often hindered by severe diffusion limitations and secondary over-cracking. This study addresses these challenges by transforming low-value natural minerals into sophisticated catalytic systems. We present a “top-down” engineering strategy for designing hierarchical catalysts based on natural Kazakhstani clinoptilolite. The multi-stage modification involves synergistic demineralization and precision chelation (EDTA, sulfosalicylic acid) to generate a tailored mesoporous architecture. This framework serves as a host for the sub-nanometric immobilization of Keggin-type heteropolyacids (PW₁₂, PMo₁₂), ensuring optimal active-phase dispersion. The innovative dual-step modification successfully bypassed the “micropore barrier”, creating a high-surface-area hierarchical network that facilitates the transport of bulky paraffinic molecules. Precise localization of heteropolyacid clusters within the created mesopores resulted in the formation of superstrong Lewis acid sites, as confirmed via temperature-programmed ammonia desorption. These sites triggered a highly efficient monomolecular beta-scission mechanism, suppressing undesirable hydrogen transfer reactions. The resulting catalysts achieved a breakthrough in technical paraffin cracking, delivering a 70% liquid product yield with an unprecedented >50% selectivity toward the C₇–C₁₄ α-olefin fraction. This work demonstrates a sustainable pathway for upgrading natural zeolites into high-performance, green catalysts that rival expensive analogs in precision and efficiency. Full article

In the renewable energy-driven “green electricity–green hydrogen–green ammonia” pathway, the development of low-temperature and low-energy-consumption ammonia synthesis technologies is of great significance. In this work, a plasma-catalytic ammonia synthesis system was established using a coaxial dielectric barrier discharge (DBD) reactor. The effects of different catalysts, including Ag, Cu, γ-Al₂O₃, BaTiO₃ and Co/BaTiO₃, Ni/BaTiO₃ on ammonia synthesis performance were systematically investigated. The reaction process was analyzed using voltage–current waveforms, Lissajous figures, and optical emission spectroscopy (OES). The results show that different catalytic systems have a significant influence on ammonia synthesis performance, with the promotional effect ranked as follows: Ni/BaTiO₃ > Co/BaTiO₃ > BaTiO₃ > Ag > γ-Al₂O₃ > Cu. Among them, Ni/BaTiO₃ exhibited the best performance. Under the conditions of N₂:H₂ = 1:1 and a gas flow rate of 2.5 L/min, the NH₃ synthesis rate reached 259.48 μmol/min, and the maximum energy efficiency reached 1.40 g-NH₃/kWh. Catalyst characterization results indicate that the BaTiO₃ support maintained a stable crystal structure, while the loaded metal species were highly dispersed and uniformly distributed on the support surface, which is beneficial for the adsorption and conversion of reactive species on the catalyst surface. Discharge characteristic analysis shows that the introduction of BaTiO₃ enhanced the local electric field and improved the uniformity of micro-discharges, while the further incorporation of metal active components strengthened the micro-discharge behavior. OES results reveal that the intensities of characteristic emission lines, such as NH, N₂⁺, and Hα, were significantly enhanced in the Ni/BaTiO₃ system, facilitating the formation and conversion of NH_x intermediates. The superior performance of Ni/BaTiO₃ is attributed to the coupling between BaTiO₃-induced dielectric enhancement and Ni-promoted surface hydrogenation and NH₃ desorption. This work provides mechanistic insight into catalyst-dependent DBD plasma-catalytic ammonia synthesis and offers an experimental basis for the further optimization of plasma-based ammonia production. Full article

In order to address corrosion and pollution problems of liquid acids and limitations of traditional solid acids, sulfated MOF-808-SO₄ catalysts were developed by creating unsaturated sites in MOF-808 for sulfate grafting with ligand defect engineering. Characterization verified framework integrity, successful sulfate coordination, and maintenance of high surface areas and tunable porosity. Temperature-programmed desorption of ammonia (NH₃-TPD) establishes a clear consistent trend between defect density and the concentration as well as the strength of acid sites, indicating that a higher degree of ligand deficiency promotes the formation of more abundant and stronger acid centers. For esterification of acetic acid with n-butanol, the catalyst prepared by replacing 40 mol% of BTC with BDC achieved ≥99% conversion of acetic acid under mild conditions of 2.0 wt% catalyst loading and 1:2 alcohol/acid molar ratio at 120 °C for 6 h, outperforming conventional solid acids. This performance stems from high-density strong Brønsted acid sites strongly coordinated at defects and an open pore structure facilitating diffusion. The catalyst was easily recovered by ethanol washing and maintained stable activity over five cycles without loss of catalytic capability. This work suggests defect engineering as an effective strategy for tuning acidity and catalytic performance in MOF-based solid acids for green esterification. Full article

With changes in the global energy structure, ammonia has emerged as a favorable hydrogen storage medium due to its excellent properties. This work details the synthesis of a barium-doped cobalt–iron alloy catalyst via subsequent heat treatment. This alloy efficiently catalyzes the decomposition of ammonia into hydrogen. The results showed that using characterization methods such as TEM and XRD indicated that adding Ba to this system could regulate the microstructure of the Co-Fe alloy. After calcination, the barium promoted a reduction in the particle size of Co-Fe nanoparticles, enabling their uniform dispersion on the surface and a more uniform dispersion and improving the accessibility of the exposed surface. The optimized catalyst (0.05Ba-0.25CoFe/CeO₂) achieved an ammonia conversion of 93.2% at 550 °C under a gas hourly space velocity of 30,000 mL·g_cat⁻¹·h⁻¹. Mechanistic analysis based on XPS and CO₂-TPD results indicated that the barium optimized the electronic structure and alkaline sites of Co-Fe, promoted the desorption of nitrogen, and thereby accelerated the reaction kinetics of ammonia decomposition. This research provides a strategic method and theoretical basis for designing high-performance non-precious metal catalysts for ammonia decomposition. Full article

Conventional ammonia production via the Haber–Bosch process is energy-intensive and carbon-heavy. Emerging biomass-based approaches offer a sustainable alternative but often lack rigorous system-level analysis based on actual reaction kinetics. This study presents a novel integrated process coupling biomass pyrolysis/gasification with Chemical Looping Ammonia Generation (CLAG) and waste heat recovery. Unlike previous models relying on simplified assumptions, this simulation incorporates experimental kinetic data for both N-absorption and N-desorption stages to ensure high fidelity. The system’s energy and mass flows were rigorously evaluated using Aspen Plus. Results indicate that the gasification stage is optimal at an O₂/biomass molar ratio of 0.2 and 750 °C. In the CLAG unit, a higher N-absorption temperature (1600 °C) and α-Al₂O₃/C ratio (3:3) significantly enhance ammonia yield. Under these optimal conditions, the system achieves a remarkably low energy consumption of 10.12 GJ/t-NH₃ and specific CO₂ emissions of 3.2 t/t-NH₃—a reduction of over 60% compared to traditional coal-based routes. The integration of waste heat recovery is identified as a critical factor in minimizing net energy input. This work validates the feasibility of the biomass-based CLAG process as a low-carbon, energy-efficient pathway for sustainable ammonia synthesis. Full article

To address the challenge of removing copper from copper–ammonia complex wastewater in the printed circuit board (PCB) industry, this study employed natural chitosan (CTS) as the base material. Dithiocarbamate (DTC) groups were grafted onto CTS, followed by further carboxylation (-COOH) to produce two novel adsorbents: DTC-CTS and DTC-CTS-COOH. The materials were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), SEM, and related techniques. The effects of solution pH, adsorption isotherms, kinetics, and regeneration performance were systematically investigated. Characterization results confirmed the successful introduction of DTC and carboxyl (-COOH) groups. Adsorption experiments demonstrated that DTC-CTS-COOH exhibited superior Cu²⁺ adsorption performance across pH 5–8, achieving a removal efficiency of (97.67 ± 1.3)% at pH 7. Its adsorption behavior followed the Langmuir model, with a maximum adsorption capacity (Q_m) of 234.8 mg·g⁻¹ at 318.15 K, significantly higher than that of DTC-CTS (183.6 mg·g⁻¹). Adsorption kinetics conformed to a pseudo-second-order model, indicating rapid adsorption rates. After five adsorption-desorption cycles, DTC-CTS-COOH maintained a Cu²⁺ removal rate above 68.41%. The synergistic interaction between -COOH and DTC functional groups enhanced the adsorbent’s capacity, rate, and pH adaptability, demonstrating that DTC-CTS-COOH holds strong potential for application in the treatment of complex copper–ammonia wastewater. Full article

The transition toward a circular economy requires innovative strategies for valorizing industrial by-products. This study investigates the potential of steelmaking furnace slag (SFS) as a low-cost adsorbent for the removal and recovery of nickel and copper ions from aqueous systems. The slag was characterized using XRF, XRD, SEM, FTIR, and thermal analyses, confirming the presence of reactive phases such as lime, periclase, and calcium silicates. Batch adsorption experiments revealed high sorption capacities (up to 147 mg·g⁻¹) and were best described by the Langmuir isotherm and pseudo-second-order kinetic model, indicating chemisorption as the rate-limiting step. FTIR and SEM analyses demonstrated the formation of nickel and copper hydroxide/oxide phases, confirming surface precipitation mechanisms. Subsequent thermal treatment produced NiO- and CuO-enriched oxide systems with photocatalytic and antibacterial potential, while hydrometallurgical recovery using ammonia solutions achieved desorption efficiencies of 90–97%. The results highlight the dual role of SFS as an efficient sorbent for wastewater pre-treatment and as a secondary source of valuable metals, contributing to sustainable materials management and circular economy goals. Full article

The conversion of polycyclic aromatic hydrocarbons (PAHs) to monocyclic aromatic hydrocarbons holds significant importance in the petrochemical and coal chemical industries, as it enables the production of high-value-added chemicals. In this study, we investigated the methane-assisted hydroconversion of PAHs to monocyclic aromatic hydrocarbons with methyl side chains over Zn-based catalysts from Hβ zeolites treated with citric acid (CA) at different concentrations. The CA-modified Hβ catalysts were characterized using X-ray diffraction (XRD), N₂ adsorption–desorption, pyridine–Fourier transform infrared spectroscopy (Py-FTIR), and ammonia temperature-programmed desorption (NH₃-TPD). The results show that low CA concentrations facilitate the removal of amorphous aluminum from the zeolite framework, thereby increasing the specific surface area, pore volume, and pore diameter of the Zn/Hβ catalyst, as well as improving its Lewis/Brønsted (L/B) acid ratio. In contrast, excessive CA treatment causes the undesirable removal of framework aluminum and leads to structural collapse in the mesoporous regions formed at the interfaces between certain crystal aggregates. This, in turn, has a negative impact on the catalyst’s specific surface area, pore volume, pore size distribution, total acidity, and L/B ratio. Experimental data further indicate that the optimal Zn/Hβ catalyst, prepared using Hβ treated with 0.08 M CA, achieves a naphthalene conversion rate of up to 99% and a benzene–toluene–xylene (BTX) selectivity of 60% in the liquid product over a 10 h reaction period. These findings confirm that CA treatment not only enhances the catalytic activity of Zn/Hβ but also significantly improves its operational stability. This work provides new insights into the rational design of catalysts for the efficient conversion of PAHs to monocyclic aromatic hydrocarbons and the utilization of methane resources. Full article

This study presents the experimental and thermodynamic evaluation of a solar thermochemical refrigeration system (STRS) powered by evacuated tube solar collectors with heat pipes as thermal energy sources, using industrial-grade BaCl₂–NH₃. The system was designed to produce refrigeration and ice using industrial-grade BaCl₂–NH₃ without additional additives or electrical input. Experimental tests were conducted under real-world conditions, with generation temperatures between 55 and 66 °C and solar irradiance of 750 to 900 W/m². The system achieved efficient ammonia desorption, yielding up to 4.2 L of refrigerant and demonstrating repeatable operation over several thermochemical cycles. During the nighttime absorption–evaporation process, the STRS reached evaporation temperatures of −7 to −3 °C and absorption temperatures between 24 and 31 °C, suitable for ice production. The internal coefficient of performance ranged from 0.244 to 0.307, with an overall efficiency of 0.146 to 0.206. The experimental data obtained were used to derive pressure–temperature equilibrium equations for the BaCl₂–NH₃ working pair, yielding correlation coefficients greater than 0.98, which confirms thermodynamic consistency. The results demonstrate that additive-free, industrial-grade BaCl₂ can achieve high efficiency at low temperatures, making this system a cost-effective and sustainable alternative for refrigeration and cold storage in rural areas. This research contributes new experimental knowledge on low-temperature thermochemical refrigeration and supports future development toward quasi-continuous optimization cycles based on experimental data. Full article

There are many obstacles to the industrial application of CO₂ hydrogenation reduction technology, the most important of which is the high economic cost. The purpose of this study is to explore the interaction mechanism between the active component CuO-ZnO-Al₂O₃(CZA) and the zeolite carrier Zeolite Socony Mobil-5(ZSM-5), screen the simplified preparation method of catalysts with high catalytic performance, and further promote the industrial application of CO₂ hydrogenation reduction technology. In this study, the effects of the gas velocity of the feedstock, the reaction temperature, the content of acidic sites in the carrier, the filling amount of active component, and the mixing mode of the active component and the carrier on catalytic CO₂ hydrogenation reduction were investigated. The structure of the catalysts was analyzed by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The catalyst surface properties were analyzed by X-ray photoelectron spectroscopy (XPS), ammonia temperature programmed desorption (NH₃-TPD), hydrogen temperature programed reduction (H₂-TPR) and other characterization methods. The research found that the grinding treatment led to the insertion of CZA between ZSM-5 zeolite particles in CZA@HZ5-20-GB, which was prepared via grinding both CZA and H-ZSM-5 with an Si/Al ratio of 20, inhibiting the action of strongly acidic sites in the zeolite, resulting in only CO and MeOH in the catalytic products, with no Dimethyl Ether (DME) generation. Full article

Cross-linked polyethylene (XLPE) has been widely used in high-voltage cables due to its superior properties, but its thermoset cross-linked structure makes it difficult to recycle. Catalytic pyrolysis offers a feasible pathway for converting XLPE into high-value chemicals. In this study, a systematic study on the catalytic cracking of XLPE using metal ion-loaded ZSM-5 nanosheets was conducted, and ZSM-5 nanosheets loaded with Ag, Mo, Ni, and Ce were prepared via ion exchange. After metal loading, ZSM-5 retained the MFI framework structure, but the specific surface area and mesopore volume varied depending on the type of metal. Temperature-Programmed Desorption of Ammonia results indicated that metal–support interactions enhanced the acidity of ZSM-5. Among the catalysts, Ag-loaded ZSM-5 exhibited the highest efficiency: with 10 wt% Ag, at 380 °C, the conversion reached 94.1%, with 52.5% light olefins in the gas phase and 59.4% benzene, toluene, and xylene (BTX) in the liquid products. Further studies on different Ag loadings revealed that moderate Ag loading (5 wt%) provided the best overall balance, maintaining 92.3% conversion, 56.1% selectivity to light olefins, and 58.2% BTX in the liquid fraction. These findings demonstrate that tuning the metal loading effectively optimizes the acidity and pore structure of ZSM-5, thereby enabling controlled regulation of XLPE pyrolysis product distribution. Full article

This study compared the effectiveness of the Sequencing Batch Biofilter Granular Reactor (SBBGR) plant with and without the integration of ozone (BIO-CHEM process) in the remediation of medium-aged landfill leachate. Special attention is given to the removal of per- and polyfluoroalkyl substances (PFAS) as a group of bioaccumulative and persistent pollutants. The findings highlight the high SBBGR performance under biological process only for key wastewater contaminants, with 82% for chemical oxygen demand (COD), 86% for total nitrogen, and 98% for ammonia. Moderate removal was observed for total (TSS) and volatile (VSS) suspended solids (41% and 44%, respectively), while phosphorus and colour removal remained limited. Remarkably, the SBBGR process achieved complete removal of long-chain PFAS, while its performance declined for shorter-chain PFAS. BIO-CHEM process significantly improved COD (87.7%), TSS (84.6%), VSS (86.7%), and colour (92–96%) removal. Conversely, ozonation led to an unexpected increase in the concentrations of several PFAS in the effluent, suggesting ozone-induced desorption from the biomass. SBBGR treatment was characterised by a low specific sludge production (SSP) value, i.e., 5–6 times less than that of conventional biological processes. SSP was further reduced during the application of the BIO-CHEM process. A key finding of this study is a critical challenge for PFAS removal in this combined treatment approach, different from other ozone-based methods. Full article

Efforts have been underway worldwide to reintroduce seawater to many historically diked salt marshes for restoration of tidal flow and associated estuarine habitat. Seawater restoration to a diked Cape Cod marsh was simulated using the computer program PHREEQC based on previously conducted microcosm experiments to better understand the associated timing and sequence of multiple biogeochemical reactions and their implications to aquatic health. Model simulations show that acidic, reducing waters with high concentrations of sorbed ferrous iron (Fe[II]), aluminum (Al), sulfide (S²⁻), ammonia (NH₄⁺ + NH₃), and phosphate (PO₄³⁻) are released through desorption and sediment weathering following salination that can disrupt aquatic habitat. Models were developed for one-dimensional reactive transport of solutes in diked, flooded (DF) marsh sediments and subaerially exposed, diked, drained (DD) sediments by curve matching porewater solute concentrations and adjusting the sedimentary organic matter (SOM) degradation rates based on the timing and magnitude of Fe(II) and S²⁻ concentrations. Simulated salination of the DD sediments, in particular, showed a large release of Al, Fe(II), NH₄⁺, and PO₄³⁻; the redox shift to reductive dissolution provided higher rates of SOM oxidation. The sediment type, iron source, and seasonal timing associated with seawater restoration can affect the chemical speciation and toxicity of constituents to aquatic habitat. The constituents of concern and their associated complex biogeochemical reactions simulated in this study are directly relevant to the increasingly common coastal marsh salination, either through tidal restoration or rising sea level. Full article