Search Results (172)

Photothermal catalytic CO₂ conversion into chemicals that provide added value represents a promising strategy for sustainable energy utilization, yet the development of highly efficient, stable, and selective catalysts remains a significant challenge. Herein, we report a rationally designed p-n junction heterostructure, T-CZ-PBA (SC), synthesized via controlled pyrolysis of high crystalline Prussian blue analogues (PBA) precursor, which integrates CuCo alloy, ZnO, N-doped carbon (NC), and Zn^II-Co^IIIPBA into a synergistic architecture. This unique configuration offers dual functional advantages: (1) the abundant heterointerfaces provide highly active sites for enhanced CO₂ and H₂ adsorption/activation, and (2) the engineered energy band structure optimizes charge separation and transport efficiency. The optimized T-C₃Z₁-PBA (SC) achieves exceptional photothermal catalytic performance, demonstrating a CO₂ conversion rate of 126.0 mmol gcat⁻¹ h⁻¹ with 98.8% CO selectivity under 350 °C light irradiation, while maintaining robust stability over 50 h of continuous operation. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) investigations have identified COOH* as a critical reaction intermediate and elucidated that photoexcitation accelerates charge carrier dynamics, thereby substantially promoting the conversion of key intermediates (CO₂* and CO*) and overall reaction kinetics. This research provides insights for engineering high-performance heterostructured catalysts by controlling interfacial and electronic structures. Full article

Leachates generated from the degradation of green waste and biosolids from urban wastewater treatment plants (WWTPs) pose significant environmental concerns due to high concentrations of organic pollutants and heavy metals. This study proposes a hybrid treatment strategy combining electrocoagulation (EC) and UVC-activated TiO₂ photocatalysis to remediate leachates produced in laboratory-scale biocells. Initial characterization revealed critical pollutant levels: COD (1373 mg/L), BOD₅ (378 mg/L), total phosphorus (90 mg/L), ammoniacal nitrogen (201 mg/L), and metals such as Ni, Pb, and Mn levels all exceeding those set out in the Ecuadorian discharge regulations. Optimized EC achieved removal efficiencies of 62.6% for COD, 44.4% for BOD₅, 89.8% for phosphorus, and 86.2% for color. However, residual contamination necessitated a subsequent photocatalytic step. Suspended TiO₂ under UVC irradiation removed up to 81.8% of the remaining COD, 88.7% of the ammoniacal nitrogen, and 94.4% of the phosphorus. Levels of heavy metals such as Zn, Fe, Pb, Mn, and Cu were reduced by over 80%, while Cr⁶⁺ was nearly eliminated. SEM–EDS analysis confirmed successful TiO₂ immobilization on sand substrates, revealing a rough, porous morphology conducive to catalyst adhesion; however, heterogeneous titanium distribution suggests the need for improved coating uniformity. These findings confirm the potential of the EC–TiO₂/UVC hybrid system as an effective and scalable approach for treating complex biocell leachates with reduced chemical consumption. Full article

5-aminotetrazole (5AT)-based gas generators, particularly the 5AT/NaIO₄ system, have garnered interest for their high gas production and energy potential. This study investigates the impact of various metal oxides (MnO₂, Al₂O₃, TiO₂, CuO, Fe₂O₃, MgO, ZnO, and MoO₃) on the thermal decomposition and combustion performance of 5AT/NaIO₄. The REAL calculation program was used to infer reaction products, which indicated that the gas products are almost all harmless, with negligibly low percentages of NO and CO. Thermogravimetric analysis revealed that metal oxides, especially MoO₃, significantly advance the decomposition process above 400 °C, reducing the activation energy by 130 kJ/mol and lowering critical ignition and thermal explosion temperatures. Combustion performance tests and closed bomb tests confirmed MoO₃’s positive effect, accelerating reaction rates and enhancing decomposition efficiency. The system’s high Gibbs free energy indicates non-spontaneous reactions. These findings provide valuable insights for designing environmentally friendly gas generators, highlighting MoO₃’s potential as an effective catalyst. Full article

Global municipal solid waste (~2B tons/year) affects sustainability, as landfill and incineration face persistent leachate contamination, demanding effective management to advance water recycling and circular economies. Accelerated investigation of hybrid biocatalytic ozonation systems is imperative to enhance contaminant removal efficiency for stringent discharge compliance. This study investigates the catalytic ozonation effects of γ-Al₂O₃-based catalysts loaded with different metals (Cu, Mn, Zn, Y, Ce, Fe, Mg) on the biochemical effluent of landfill leachate. The catalysts were synthesized via a mixed method and subsequently characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). Pseudo-second-order kinetics revealed active metal loading’s impact on adsorption capacity, with Cu/γ-Al₂O₃ and Mg/γ-Al₂O₃ achieving the highest Q_e (0.85). To elucidate differential degradation performance among the catalysts, the ozone/oxygen gas mixture was introduced at a controlled flow rate. Experimental results demonstrate that the Cu/γ-Al₂O₃ catalyst, exhibiting optimal comprehensive degradation performance, achieved COD and TOC removal efficiencies of 84.5% and 70.9%, respectively. UV–vis absorbance ratios revealed the following catalytic disparities: Mg/γ-Al₂O₃ achieved the highest aromatic compound removal efficiency; Ce/γ-Al₂O₃ excelled in macromolecular organics degradation. EEM-PARAFAC analysis revealed differential fluorophore removal: Cu/γ-Al₂O₃ exhibited broad efficacy across all five components, while Mg/γ-Al₂O₃ demonstrated optimal removal of C2 and C4, but showed limited efficacy toward C5. These findings provide important insights into selecting catalysts in practical engineering applications for landfill leachate treatment. This study aims to elucidate catalyst formulation-dependent degradation disparities, guiding water quality-specific catalyst selection to ultimately enhance catalytic ozonation efficiency. Full article

The hydrogenation of CO₂ to methanol is an effective approach for utilizing carbon resources. Cu-ZnO-based catalysts have attracted significant attention due to their ability to activate CO₂; however, improving methanol selectivity remains a challenge. In this study, the incorporation of an appropriate amount of Ga into Cu-ZnO catalysts, resulting in the formation of spinel ZnGa₂O₄ crystals, significantly enhances the conversion of CO₂ to methanol. Ternary CuZnGa composite oxides with varying Ga contents were synthesized, and their effects on CO₂ hydrogenation were investigated. The optimal Cu₆Zn₃Ga₁ catalyst achieved a CO₂ conversion rate of 13% and a methanol selectivity of 59% under reaction conditions of 240 °C, 4 MPa, and a GHSV of 7500 mL⋅g_cat⁻¹⋅h⁻¹. In contrast, the undoped Cu₆Zn₄ catalyst exhibited a lower CO₂ conversion of 9.8% and a methanol selectivity of 38%. Characterization results indicate that the introduction of Ga promotes the formation of oxygen vacancies, enhances CO₂ activation, and facilitates electronic interactions between spinel ZnGa₂O₄ and Cu sites, thereby improving methanol production. Furthermore, the spinel ZnGa₂O₄-modified Cu catalyst demonstrated excellent stability over 90 h of continuous operation. This study presents a novel approach to designing spinel ZnGa₂O₄-modified Cu-ZnO-based catalysts and offers a new strategy for enhancing CO₂ hydrogenation to methanol. Full article

This research aimed to enhance biodiesel stability through catalytic transfer hydrogenation using a biomimetic bimetallic catalyst and glycerol as a hydrogen donor. The effects of catalyst species, intermediate solvent, glycerol feed, and glycerol form on biodiesel stability were investigated. In this study, the examined bimetallic catalysts were Zn-Cr-bicarbonate, Zn-Cr-formate, Zn-Cr-Ni, and Cu-Ni/SiO₂. Based on the results, the most excellent catalyst was presented by Cu-Ni/SiO₂ catalyst with DMF solvent and 10 wt% glycerol feed. This combination demonstrated a significant reduction in iodine (ΔIV = −4.9 g-I₂/100 g) and peroxide values (ΔPV = −5.2 meq-O₂/kg) accompanied by an elevation of oxidative stability (ΔOS = 4.3 h). Moreover, the reaction of catalytic transfer hydrogenation using these bimetallic catalysts followed the theoretical mechanism of the simultaneous dehydrogenation–hydrogenation process with two different metals. The promotion of bicarbonate and formate ions on the bimetallic catalyst provided hydrogen transfer assistance in the catalyst. Hence, the continuous improvement of biodiesel properties is expected to promote sustainable implementation of cleaner diesel fuel. Full article

This study focuses on optimizing the Reverse Water Gas Shift (RWGS) reaction system using a membrane reactor to improve CO₂ conversion efficiency. A one-dimensional simulation model was developed using FlexPDE Professional Version 8.01/W64 software to analyze the performance of ZSM-5 membranes integrated with 0.5 wt% Ru-Cu/ZnO/Al₂O₃ catalysts. The results show that the membrane reactor significantly outperforms the conventional Packed Bed Reactor by achieving higher CO₂ conversion (0.61 vs. 0.99 with optimized parameters), especially at lower temperatures, due to its ability to remove H₂O and shift the reaction equilibrium selectively. Key operational parameters, including temperature, pressure, and sweep gas flow rate, were optimized to maximize membrane reactor performance. The ZSM-5 membrane showed strong H₂O selectivity, with an optimum operating temperature of around 400–600 °C. The problem is that many reactants permeate at higher temperatures. Subsequently, a Half-MPBR design was introduced. This design was able to overcome the reactant permeation problem and increase the conversion. The conversion ratios for PBR, MPBR, and Half-MPBR are 0.71, 0.75, and 0.86, respectively. This work highlights the potential of membrane reactors to overcome the thermodynamic limitations of RWGS reactions and provides valuable insights to advance Carbon Capture and Utilization technologies. Full article

The thermocatalytic hydrogenation of CO₂ to methanol offers a promising route for reducing greenhouse gas emissions (GHG) and producing valuable chemicals and fuels. In this study, copper–zinc bimetallic catalysts supported on a zirconium-based MOF-808 framework were synthesized via a facile deposition–precipitation method and compared to a conventional Cu/ZnO/Al₂O₃ (CZA) catalyst. MOF-808 was selected due to its high surface area and porous structure, which enhance metal dispersion. Characterization through X-ray diffraction (XRD) and N₂ physisorption showed significant changes in surface area and pore structure after Cu-Zn incorporation and calcination. The 50-CuZn MOF-808 catalyst achieved the best catalytic performance at 260 °C and 40 bar, demonstrating a high STY of 193.32 gMeOH·Kgcat⁻¹ h⁻¹ and a turnover frequency (TOF) of 47.44 h⁻¹, surpassing traditional CZA catalysts. The strong Cu-Zn-Zr interactions within the MOF-808 framework played a crucial role in promoting CO₂ activation and methanol formation. This study underscores the potential of MOF-808-supported Cu-Zn catalysts as viable alternatives to traditional systems for CO₂ hydrogenation to methanol. Full article

Layered double hydroxide (LDH)-derived mixed oxides offer a promising approach for CO₂ hydrogenation to light hydrocarbons. Herein, we explore the impact of various transition metals (X = Mn, Co, Cu, and Zn) incorporated into the M-Al or M-(Al+Fe) LDH structures, with the aim of exploring possible synergistic effects. Structural and compositional analyses reveal that an abundance of Fe over Al (Fe/Al ratio ~4) leads to the formation of mixed oxide crystalline phases attributed to CoFe₂O₄, CuFe₂O₄, and ZnFe₂O₄. Catalytic evaluation results demonstrate that the X-Al LDH-derived oxides exhibit high CO₂ conversion yet are selective to CH₄ or CO. In contrast, Fe incorporation shifts selectivity toward higher hydrocarbons. Specifically, the yield to higher hydrocarbons (C₂⁺) follows the order Ζn-Al-Fe > Cu-Al-Fe > Mn-Al-Fe > Co-Al-Fe >> Mn-Al, Co-Al, Zn-Al, Cu-Al, highlighting the pivotal role of Fe. Moreover, Zn-Al-Fe and Mn-Al-Fe catalysts have been shown to be the most selective towards light olefins. Zn-based systems also exhibit high thermal and structural stability with minimal coke formation, whereas Co-, Cu-, and Mn-based catalysts, when modified with Fe, experience increased carbon deposition or structural changes that may impact long-term stability. This work provides insights into the combined role of Fe and a second transition metal in LDHs for modulating catalytic activity, phase transformations, and stability, underscoring the need for further optimization to balance selectivity and catalyst durability in CO₂ hydrogenation applications. Full article

The oxidation of 1,2-propanediol (1,2-PDO) under alkaline heterogeneous catalysis can be optimized to produce lactic acid, a valuable commodity chemical. In this study, Pd nanoparticles supported on various metal oxides (CeO₂, CuO, ZrO₂, ZnO, SnO₂) were synthesized via a wet-chemistry method. Furthermore, CeO₂-supported Pd nanoparticle catalysts were prepared using different reduction methods. The catalytic performance for the selective oxidation of 1,2-PDO was evaluated using a range of characterization techniques. Under optimal conditions (120 °C, 1.0 MPa O₂ pressure, 2 h reaction time, and a NaOH/1,2-PDO molar ratio of 3.0), a high lactic acid yield of 62.7% was achieved. Single-factor experiments revealed that lactic acid selectivity decreased with prolonged reaction time. Conversely, increasing temperature, NaOH concentration, and O₂ pressure initially enhanced lactic acid selectivity, but further increases resulted in a decline. Physicochemical characterization revealed that different supports and reduction methods affect the basicity of the catalyst, which subsequently influences the selectivity of the target product, lactic acid. Full article

The CuZnOAl₂O₃ catalyst shows excellent activity and selectivity in the reaction of CO₂ hydrogenation to methanol as a consequence of its controllable physicochemical properties, which is expected to offer an efficient route to renewable energy. In this study, CuZnOAl₂O₃ catalysts are engineered by a special pretreatment, constructing a carbonate structure on the surface of the catalyst. Compared to the unmodified catalyst, the optimized catalyst (CZA-H-C1) not only exhibits an improved methanol selectivity of 62.5% (250 °C and 3 MPa) but also retains a minimal degree of deactivation of 9.57% over a 100 h period. By characterizing the catalysts with XRD, TEM, XPS and in situ DRIFTS spectroscopy, it was found that the surface carbonate species on Cu-based catalysts could significantly enhance the reaction and shield the active sites. This study offers theoretical insights and practical strategies for the rational design and optimization of high-performance heterogeneous catalysts. Full article

The development of effective photocatalysts for environmental applications is still a critical aspect of green chemistry. This study explores copper oxide (Cu_xO) catalysts supported on titanium dioxide (TiO₂) and zinc oxide (ZnO) for the photocatalytic reduction of maleic acid to succinic acid under ultraviolet (UV) light in water. The main goal was to evaluate the performance of CuO/ZnO compared to CuO/TiO₂ in photoreduction. In order to improve the efficiency of the first catalyst, an environmentally friendly synthesis, assisted by polydopamine (PDA), was tested, obtaining the Cu₂O/ZnO-PDA catalyst. The results showed that CuO/TiO₂ exhibited the highest activity for maleic acid reduction, obtaining a succinic acid yield and a selectivity of 32% after 24 h of reaction time, but comparable results could be reached even with Cu₂O/ZnO-PDA increasing the reaction time. Furthermore, the addition of sodium ascorbate as a co-catalyst in the reaction mixture allowed us to overtake the previous results, leading to a succinic acid yield of 61% and a selectivity of 67%. These findings suggest that the PDA shell can be a solution for Cu_xO photodegradation, making Cu₂O/ZnO-PDA an alternative to the toxic CuO/TiO₂. Full article

This study investigates the environmental significance of ciprofloxacin as an emerging contaminant and the need for effective degradation methods. The chemical coprecipitation method was used in this study to prepare the Zn-Cu-Ni composite silicate, serving as a heterogeneous ozonation catalyst. The catalytic activity was then evaluated by degrading ciprofloxacin (CIP). Scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, nitrogen adsorption–desorption, and Fourier transform infrared analysis (FTIR) were used to characterize the Zn-Cu-Ni composite silicate. The catalyst had a high surface area (308.137 m²/g), no regular morphology, and a particle size of 7.6 µm and contained Si-O-Si, Ni-O-Si, and Zn-O-Si. The results showed that the CIP degradation and mineralization rates (pH 7.0, CIP 3.0 mg/L, Ozone 1.5 mg/L) were significantly enhanced in the presence of the Zn-Cu-Ni composite silicate. The CIP and total organic carbon (TOC) removal rates were increased by 51.09% and 18.72%, respectively, under optimal conditions, compared with ozonation alone. The adsorption of Zn-Cu-Ni composite silicate, ozone oxidation, and ·OH oxidation synergistically promoted the efficient removal of CIP. This study provides valuable catalytic ozone technology for degradation of antibiotics in wastewater to reduce environmental pollution with potential practical applications. Full article

Compared with the traditional granular catalyst, a mesh-type structured CuZn-based catalyst prepared by the self-growth ordered nanoporous carrier γ-Al₂O₃/Al can adapt to the MSR reaction system with high flux, strong mass transfer and heat transfer, and can promote the practical process. In this study, the kinetic experiment using a CuZn-based structured catalyst was carried out, and a nonlinear single-rate PL model was established. Based on this, a 3D theoretical model of the MSR reformer was drawn in COMSOL Multiphysics. By changing the stacking form and mesh shape of the catalyst to construct the flow channel, the chemical reaction process, heat transfer process, and mass transfer process of the CuZn structured catalyst in the reformer under different flow channels are further simulated, which provides a theoretical basis for studying the enhancement of the MSR reaction and the development of a supporting micro hydrogen production system. Full article

Due to the growth of biodiesel production, utilization of the glycerol formed as a by-product is still of considerable importance. This study is devoted to a novel approach for glycerol hydrogenolysis with use of in situ generated Cu-ZnO catalysts. The main product formed is 1,2-propanediol, with the by-products being lactic acid and ethylene glycol. The Cu-ZnO catalysts are characterized by AAS, XRD, XPS, SEM, TEM, EDX, BET, and chemisorption N₂O. The proportion of ZnO turns out to have a significant effect on the activity and selectivity of the catalyst formed. Increasing the ZnO content enables one to obtain more dispersed, active, selective, and agglomeration-resistant catalysts. The transition from monometallic Cu catalysts to Cu-ZnO with a ZnO content of 65 wt% allows one to increase selectivity from 74 to 86%, TOF from 0.136 to 0.511 s⁻¹, and S_Cu from 1.9 to 7.1 m²/g-Cu. The morphology of the synthesized Cu-ZnO catalysts resembles the structure of oxide/metal inverse catalysts. Full article