Search Results (715)

The removal of sulfur compounds such as ethyl mercaptan from natural gas remains a critical challenge due to their detrimental effects on downstream processes, catalyst poisoning, and environmental emissions. In this study, a series of halloysite-supported transition metal oxide catalysts was synthesized and evaluated for the removal of sulfur compounds from natural gas at 25 °C, 200 psi, and 36 mL/min, using 0.5 g of the catalyst. The nanotubular structure and dual surface chemistry of halloysite promote enhanced metal dispersion and improved mass transfer. Single-metal (manganese, copper, zinc, and nickel) catalysts were developed and tested, after which a multi-metal oxide (base) catalyst comprising a composite of the single metals (Zn-Cu-Mn-Ni) was developed as a base catalyst to combine adsorption-active and redox-active functionalities, and its performance was further enhanced by the addition of palladium as promoter. A combination of analytical techniques, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red spectroscopy (FTIR), Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS), provided evidence that highly dispersed metal oxide phases were formed and the halloysite structure was preserved. XPS data showed the presence of oxidation states of metals that were active (Zn²⁺, Cu²⁺, Ni²⁺, Mn³⁺/Mn⁴⁺ and Pd²⁺), an indication of a redox-active surface for sulfur interaction. Results from the breakthrough experiments showed that the base catalyst significantly improved sulfur removal compared to single-metal catalysts, while the Pd-promoted catalyst exhibited the highest performance, with a breakthrough time of 630 min. Palladium was incorporated at low loading as a promoter, enhancing adsorption performance while maintaining a favorable balance between efficiency and material cost. This enhancement is attributed to synergistic interactions between adsorption-active sites and redox-active species, as well as improved electron transfer facilitated by palladium. The results demonstrate that rational design of multi-metal oxide catalysts supported on naturally occurring halloysite provides an effective and scalable approach for sulfur removal from natural gas, with strong potential for industrial applications. Full article

The massive discharge of methylene blue causes severe water pollution, and the development of efficient and stable heterogeneous Fenton catalysts is crucial for wastewater treatment. To address the shortcomings of traditional iron-based amorphous catalysts, such as low activity and poor stability, this study employed Fe₈₀Si₆B₁₀Cu₁Nb₃ five-component amorphous alloy as the catalyst to investigate its catalytic degradation performance, cyclic stability, and catalytic mechanism for MB. Batch experiments, SEM, XRD characterization, and kinetic fitting were combined to carry out the research. The results showed that under the optimal conditions (25 °C, pH = 3, H₂O₂ concentration of 5 mM, catalyst dosage of 0.5 g/L), the catalyst could completely degrade methylene blue within 9 min with a reaction rate constant k_obs of 0.44 min⁻¹, and the degradation efficiency showed no obvious attenuation after 20 consecutive cyclic degradation runs. After degradation, slight selective corrosion occurred on the catalyst surface, while the amorphous structure of the matrix remained stable. This study confirms that the Cu/Nb dual synergy improves the catalytic performance and stability, clarifies the relevant catalytic mechanism, and provides theoretical and technical support for the design of high-performance iron-based amorphous catalysts and the treatment of dye-containing wastewater. Full article

This work presents a novel one-step plasma–solution synthesis of Prussian Blue (PB) and copper hexacyanoferrate (Cu-PBA) nanoparticles via underwater pulsed DC discharge. For the first time, the direct plasma-assisted formation of these coordination polymers is reported. The obtained materials were examined by X-ray diffraction, Fourier-transform infrared spectroscopy, Raman spectroscopy, and scanning electron microscopy (SEM). These analyses confirmed that the desired phases had formed, along with small amounts of oxide byproducts (α-Fe₂O₃, CuO) arising from the erosion of the electrodes. Photocatalytic activity was evaluated through the degradation of organic dyes (Reactive Red 6C, Rhodamine B, and Methylene Blue) under UV-light irradiation. Both catalysts achieved complete dye degradation within 90 min of UV irradiation (after an initial 30 min dark adsorption step, total experiment time 120 min). Notably, selective performance was observed: PB exhibited higher activity toward the cationic dye Methylene Blue, while Cu-PBA was more effective for the anionic dye Reactive Red 6C. This selectivity is attributed to the specific oxide impurities forming heterojunctions that facilitate charge separation and generate distinct reactive oxygen species. The plasma–liquid method offers a rapid and environmentally benign route to functional PBA-based composites, with potentially scalable characteristics pending further engineering optimization. These findings highlight the potential of utilizing synthesis-induced impurities to tailor photocatalytic selectivity for water purification applications. Full article

Sulfur is a well-known catalyst poison, particularly for catalysts based on transition metals. Herein, we studied the adsorption of sulfur species on small nanoparticles (~1 nm in size) of the face centered cubic (fcc) transition metals (Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au) using density functional theory (DFT) modeling. At low sulfur coverage (one S atom per nanoparticle), sulfur preferentially occupies the surface hollow sites of the nanoparticles. At higher coverage, however, the subsurface diffusion of S in Ni, Pd, and Ag nanoparticles becomes energetically favorable with low activation energies. Among the considered metals, sulfur binds most strongly to Rh and Ir, and most weakly to Ag and Au. The present results shed light on the facility of S-poisoning on such metal nanoparticles, either by surface blocking or by underlying sulfurization of the metal. Full article

Here, we report a highly efficient and stable catalytic system based on monometallic oxides supported on HY zeolites for the catalytic oxidation of chlorobenzene (CB). Among the transition and rare-earth metal oxides screened, the 30Cu/HY catalyst demonstrates exceptional performance, achieving near 100% CB conversion at 300 °C (500 ppm CB, 10,000 h⁻¹) alongside outstanding 24 h continuous stability without deactivation. Quantitative Py-IR analysis reveals that this superior activity is fundamentally driven by extensive solid-state ion exchange, forming robust Lewis acid centers (Cu-Y structures) that synergize with zeolitic Brønsted acid sites to efficiently polarize and cleave C-Cl bonds. Through an integrated approach combining in situ DRIFTS, real-time mass spectrometry, TGA, and NLDFT pore size analysis, we elucidate that the exceptional deep-oxidation capability of Cu/HY continuously mineralizes carbonaceous intermediates. This property minimizes coke deposition (2.91 wt%) and preserves the hierarchical pore architecture, preventing the coverage of active sites and severe pore blockage by partially oxidized intermediates (such as phenolic, aldehydic, and quinonic species) and stable carbonate species responsible for the deactivation of other metal oxides. These insights provide a mechanistic framework for the rational design of robust, chlorine-resistant catalysts for the sustainable abatement of persistent organic pollutants. Full article

Formic acid (FA) has emerged as a promising liquid hydrogen storage material, yet efficient photothermal dehydrogenation catalysts with high activity and H₂ selectivity remain challenging. Herein, a polymetallic synergistic PdCu/M-ZNC (where M represents the co-doped In, Sn and Mo species) is fabricated by molten-salt-assisted pyrolysis of ZIF-8 precursors followed by metal incorporation. The unique molten salt environment effectively preserves the porous architecture of ZIF-8, enabling the secure anchoring of PdCu alloy nanoparticles onto the carbonaceous matrix enriched with M-N_x coordination sites. Under light irradiation, the PdCu alloy sites kinetically accelerated the overall adsorption and activation of FA molecules. Based on empirical observations and corroborated by the established literature, this alloying effect was inferred to facilitate the C-H bond cleavage and HCOO* desorption processes. Concurrently, the M-N_x sites act as efficient electron transfer channels, facilitating the rapid coupling of photogenerated electrons with protons (H⁺) to evolve H₂. Consequently, the optimal catalyst exhibits an enhancement in gaseous product yield (404.46 mmol/g/h) and H₂ selectivity (67.49%) at 75 °C. This work offers a catalyst design that aligns with several principles of green chemistry: it maximizes the atom utilization of precious Pd, incorporates synergistic non-precious metals within MOF-derived frameworks to enhance stability, and leverages solar energy to drive hydrogen production under mild conditions, presenting a more sustainable pathway for hydrogen release from liquid carriers. Full article

The co-pyrolysis of Chlorella vulgaris (CV) and Eucalyptus branches (EP) offers a promising strategy to enhance bio-oil yield, improve resource utilization efficiency, and alleviate environmental pressures. In this study, the microwave-assisted co-pyrolysis of CV and EP at a mass ratio of 2:1 was investigated, focusing on the catalytic performance of Ni-X (X = Mg, Cu, Fe) bimetallic modified HZSM-5 zeolites. The effects of these catalysts on pyrolysis characteristics, product distribution, and bio-oil composition were systematically evaluated. Experimental results showed that the 15% Ni-Cu/HZSM-5 catalyst exhibited the best catalytic performance, achieving the highest bio-oil yield of 16.83%; it also elevated the R_m to 0.0687 wt.%/s and reduced T_s to 2084 s. Composition analysis revealed that Ni-Cu/HZSM-5 significantly promoted the formation of hydrocarbons, increasing their relative content from 11.59% (C2E1 Group) to 28.92%, while effectively suppressing the formation of nitrogen-containing compounds, reducing their content by 5.05%. Based on these results, a possible reaction pathway is proposed in which the Ni-Cu/HZSM-5 catalyst may enhance heteroatom removal through hydrodeoxygenation (HDO) at the Ni-Cu sites, followed by cracking and aromatization at the HZSM-5 acid sites. This effect may be complemented by preferential adsorption of oxygenated intermediates over nitrogen-containing species, which could help suppress the formation of nitrogenous heterocycles. This work provides theoretical guidance for the application of bimetallic zeolite catalysts in microalgae/lignocellulose co-pyrolysis, alongside a viable pathway for valorizing Eucalyptus by-products to produce high-quality bio-oil. Full article

Carbon monoxide (CO) is a highly toxic, colorless, and odorless gas posing significant risks to human health and the environment. Catalytic oxidation offers a promising, economically viable solution by converting CO into nontoxic CO₂ under mild conditions without energy-intensive regeneration. However, existing MnO₂-based catalysts often exhibit poor activity and stability in harsh environments, particularly at low temperatures and high humidity. In this study, we propose a Cu²⁺ ion-exchange modification strategy to activate lattice oxygen species in δ-MnO₂, thereby significantly enhancing its low-temperature CO oxidation performance. Structural characterization by XRD and SEM confirms that Cu-doped δ-MnO₂ retains its original birnessite-type structure and porous morphology. ICP-OES and XPS analyses verify that Cu²⁺ ions effectively replace interlayer K⁺ ions. The resulting MnO₂-150Cu catalyst demonstrates exceptional activity, achieving 100% CO conversion at 40 °C in dry air and maintaining full conversion at 80 °C in the presence of 1.3 vol.% H₂O at a weight hourly space velocity of 150 L/g·h. H₂-TPR and O₂-TPD results confirm that Cu doping enhances the reducibility and mobility of lattice oxygen. Furthermore, in situ DRIFTS analysis reveals that the migration of active oxygen species is the rate-limiting step at low temperatures. This work provides a novel and effective strategy for activating lattice oxygen in MnO₂-based catalysts, offering a promising pathway for developing high-performance materials for low-temperature CO oxidation under practical environmental conditions. Full article

This work investigates the behavior of carbon dioxide (CO₂) near the surface of different single-atom alloys to evaluate their potential as catalysts for decarbonization processes. Specifically, 26 transition metals from the first three transition series, alloyed with three low Miller index copper supports, were considered. Adsorption energies and distances of linear CO₂, trigonal CO₂, and CO* + O* on the surfaces were calculated using the semiempirical computational method MOPAC-PM7. Additionally, activation energies were determined from previously published research. The proposed methodology is less computationally demanding than DFT studies, and results show good agreement with both experimental and simulated data. This approach provides a computationally efficient methodology for screening promising materials that convert CO₂ into valuable products, such as methane and methanol. Full article

Synthetic dyes frequently persist through conventional wastewater treatment, motivating the use of advanced oxidation processes capable of breaking down these stable molecules. Metal-doped carbon dots (CDs) offer a tuneable platform for catalytic dye degradation in water, although their performance varies strongly with operating conditions. The aim of this work was to determine how temperature, H₂O₂ dosage, and pH influence the catalytic behaviour of Fe-, Cu-, Zn-, and Mg-doped CDs during the degradation of methylene blue (MB) and rhodamine B (RB), optimised using a Taguchi L27 orthogonal array design. Temperature and oxidant loading were the dominant factors: higher temperatures accelerated reactions through Arrhenius-type kinetics, while increasing H₂O₂ availability improved removal until excessive levels began to suppress •OH generation. Across all condition sets, apparent rate constants spanned 7.0 × 10⁻⁴–2.65 × 10⁻² min⁻¹, with t₅₀ values of 26–217 min and t₉₀ extending from ~86 min to >700 min; final decolourisation ranged from ~17% to nearly 100%. pH played a secondary role, mainly affecting dye speciation and surface adsorption. Dopant identity shifted the optimum operating region for each catalyst: Fe- and Cu-CDs achieved complete or near-complete removal of both dyes at pH 7 and 50 °C with relatively low H₂O₂ dosage (0.5–1.0 mL); Zn-CDs reached equivalent performance at pH 7 and 25 °C but required higher oxidant loading (1.5 mL of H₂O₂), reflecting their photo-induced rather than thermally driven activation mechanism; Mg-CDs performed comparably under the same conditions as Fe- and Cu-CDs. The resulting condition–catalyst map highlights the operating regimes that maximise efficiency while minimising chemical input, providing a practical framework for selecting carbon-dot-based catalysts for water treatment applications. Full article

The development of efficient, sustainable, and low-cost catalysts for wastewater treatment remains a major environmental challenge. In this work, Zn-doped CuO nanostructures were successfully synthesized via a green route using Aloysia citrodora leaf extract as a natural reducing and stabilizing agent. The structural and morphological properties of the prepared catalysts were systematically characterized by XRD, Raman spectroscopy, FTIR, SEM, and EDX analyses. The results revealed the formation of highly crystalline monoclinic CuO nanoparticles, whose defect density and surface properties were significantly modified by Zn incorporation. The catalytic performance of the synthesized materials was evaluated through the heterogeneous Fenton-like degradation of Rhodamine B in aqueous solution under dark conditions. The Zn-doped CuO catalyst exhibited outstanding degradation efficiency (~99.97%) within only 30 min, using a low catalyst dosage of 15 mg and a minimal H₂O₂ amount of 25 μL. The enhanced catalytic activity is attributed to the synergistic interaction between Zn-induced lattice defects and the Cu²⁺/Cu⁺ redox cycle, which promotes efficient H₂O₂ activation and •OH radical generation. Radical scavenging experiments confirmed the dominant role of hydroxyl radicals in the degradation process. Compared with previously reported CuO-based catalysts, the present system demonstrates superior performance in terms of reaction rate, oxidant consumption, and energy efficiency. These findings highlight the potential of Zn-doped CuO synthesized via green chemistry as a promising and sustainable catalyst for advanced wastewater treatment applications. Full article

CuCo-based catalysts are promising candidates for higher alcohol synthesis from syngas, yet their performance is often limited by poor metal dispersion and insufficient Cu-Co synergy. In this work, a series of ordered mesoporous CuCoAl catalysts with varying Cu/Co atomic ratios were synthesized via the evaporation-induced self-assembly (EISA) method. The structural, electronic, and catalytic properties were systematically investigated using N₂ physisorption, XRD, TEM, H₂-TPR, CO-TPD, XPS, and fixed-bed reactor evaluation. The results show that all CuCoAl catalysts prepared by the EISA method possess well-ordered mesoporous structures with high surface areas (up to 235 m²/g) and narrow pore size distributions. The interaction between Cu and Co stabilizes the mesoporous framework, inhibits Cu particle growth, and induces electron transfer from Cu to Co as evidenced by XPS. Among the catalysts tested, Cu₁Co₁Al (Cu/Co = 1:1) exhibits the highest strong CO adsorption capacity (1.54 mmol/g) and surface hydroxyl content (63.29%), achieving a CO conversion of 32.9% with a C₂⁺ alcohol space–time yield of 20.5 mg·gcat⁻¹·h⁻¹. These findings establish clear structure–performance relationships for ordered mesoporous CuCoAl catalysts and provide fundamental guidance for the rational design of efficient catalysts for higher alcohol synthesis. Full article

This study evaluated the efficiency and ecotoxicological impact of the Fenton oxidation process with different metal-based catalysts (FeSO₄, CuSO₄, MnSO₄) in removing pharmaceuticals and organic contaminants from real hospital wastewater. All catalytic systems achieved high oxidation, with COD reduction reaching 81–89% after 4 h. Two complementary approaches were applied: targeted LC-MS/MS quantification of a model mixture of antibiotics and pharmaceuticals, and untargeted GC-MS/MS screening method for assessing the overall organic contaminant profile. Toxicity was assessed using Microtox^®. Targeted analysis showed complete or near-complete degradation of β-lactams, tetracyclines and most sulfonamides, with slightly lower removal for sulfamethoxazole in FeSO₄ system (96%). Fluoroquinolones and selected pharmaceuticals, such as caffeine and propranolol were more resistant, particularly with CuSO₄ and MnSO₄ catalysts. The untargeted GC-MS/MS screening revealed the highest overall reduction in chromatographic peak areas for FeSO₄ (70%), followed by MnSO₄ (39%) and CuSO₄ (36%). GC-MS/MS profiling confirmed that the Fe-catalyzed process was the most effective in reducing the total chromatographic peak area (70%). However, ecotoxicological assays revealed a significant increase in toxicity post-treatment, with growth inhibition of Allivibrio fischeri reaching 98%. This suggests that high oxidation does not directly correlate with biological safety, likely due to the presence of unconsumed reagents or the formation of transformation products with higher acute toxicity. These findings emphasize the necessity of integrating bioassays into treatment evaluation protocols to assess the true environmental risk of treated effluents. Full article

Catalysis has entered everyday life through a range of technological processes that rely on different catalytic systems. The increasing demand for such systems requires rationalization of the use of their expensive components, such as noble-metal catalysts. As such, a catalyst with low noble-metal concentration, in which each one of the noble atoms is active, would reach the lowest price possible. Nevertheless, no clear reactivity descriptors have been outlined for this type of low-coordinated supported atom. Using DFT calculations, we consider three diverse systems as models of single-atom catalysts. We investigate monomers and bimetallic dimers of Ru, Rh, Pd, Ir, and Pt on MgO(001), Cu adatom on thin Mo(001)-supported films (NaF, MgO, and ScN), and single Pt adatoms on oxidized graphene surfaces. The reactivity of these metal atoms was probed by CO. In each case, we see the interaction through the donation–backdonation mechanism. In some cases, CO adsorption energies can be linked to the position of the d-band center and the adatom’s charge. A higher-lying d-band center and less-charged, supported single atoms bind CO more weakly. Also, in some cases, metal atoms that are less strongly bound to the substrate bind CO more strongly. The results suggest that the identification of common activity descriptor(s) for single metal atoms on foreign supports is a difficult task with no unique solution. However, it is also suggested that the stability of adatoms and strong anchoring to the support are prerequisites for the application of descriptor-based search to novel single-atom catalysts. Full article

The electrochemical reduction of CO₂ offers a sustainable approach to transforming carbon dioxide into value-added products when powered by renewable energy. However, current electrocatalysts lack efficiency and selectivity, hindering commercial application. Combining tin’s high formate selectivity with copper’s ability to reduce CO₂ via COOH* pathway offers a promising strategy. This synergy mitigates copper’s low selectivity, providing a cost-effective catalyst with enhanced performance over pure Sn-based systems. This work investigates CuSn bimetallic electrocatalysts synthesised by scalable electrodeposition onto gas diffusion layers to boost formate production. Catalytic performance and cell potential were evaluated at current densities ranging from 50 to 200 mA cm⁻² and varying Sn compositions. Catalysts with Sn content below 4% predominantly formed CO and H₂, but smaller particles and improved metal dispersion increased formate production. A catalyst containing 12% Sn achieved a maximum faradaic efficiency (FE) of 52% at 50 mA cm⁻² with an iR-corrected potential of −0.56 V vs. SHE. At 200 mA cm⁻², it exhibited a 30% FE for formate, along with 31% FE for CO and 9.3% FE for H₂, while other gases contributed to less than 4% FE, indicating potential as syngas feedstock. Higher Sn content, combined with smaller, well-distributed particles, effectively suppressed H₂, CO, and other by-products, highlighting a strong dependence of FE on Sn content and bimetallic distribution, demonstrating compositional tuning importance via electrodeposition. Full article