Search Results (46)

This study addresses the efficiency and cost challenges of hydrogen evolution reaction (HER) catalysts in the context of carbon neutrality strategies by employing a synergistic approach that combines cation vacancy anchoring and transition metal doping on two-dimensional (2D) MXenes. Using an in situ LiF/HCl etching process, the aluminum layers in Ti₃AlC₂ were precisely removed, resulting in a few-layer Ti₃C₂T_x MXene with an increased interlayer spacing of 12.3 Å. Doping with the transition metals Fe, Co, Ni, and Cu demonstrated that Fe@Ti₃C₂ provided the optimal HER performance, characterized by an overpotential (η₁₀) of 81 mV at 10 mA cm⁻², a low Tafel slope of 33.03 mV dec⁻¹, and the lowest charge transfer resistance (R_ct = 5.6 Ω cm²). Mechanistic investigations revealed that Fe’s 3d⁶ electrons induce an upward shift in the d-band center of MXene, improving hydrogen adsorption free energy and reducing lattice distortion. This research lays a solid foundation for the design of non-precious metal catalysts using MXenes and highlights future avenues in bimetallic synergy and scalability. Full article

The oxidation of glycerol offers a valuable route for producing high-value chemicals. This review provides an in-depth analysis of the current advancements and mechanistic insights into novel metal-based catalysts for glycerol oxidation. We discuss the catalytic roles of both precious metals (e.g., Pt, Pd, Au), noted for their high efficiency and selectivity, and cost-effective alternatives, such as Ni, Cu, and Fe. Bimetallic and metal oxide catalysts are highlighted, emphasizing synergistic effects that enhance catalytic performance. This review elucidates the key mechanism involving selective adsorption and oxidation, providing detailed insights from advanced spectroscopic and computational studies into the activation of glycerol and stabilization of key intermediates, including glyceraldehyde and dihydroxyacetone. Additionally, selective carbon–carbon bond cleavage to yield smaller, valuable molecules is addressed. Finally, we outline future research directions, emphasizing the development of innovative catalysts, deeper mechanistic understanding, and sustainable process scale-up, ultimately advancing efficient, selective, and environmentally friendly catalytic systems for glycerol valorization. Full article

Catalytic combustion is an efficient and economic technology for eliminating volatile organic compounds (VOCs) in industrial environments. This study evaluated the synergistic catalytic properties of bimetallic oxides, viz., CoM/γ-Al₂O₃ (M = Cu, Fe, or Ni), for improving the combustion efficiency of toluene. The CoM/γ-Al₂O₃ catalysts were prepared by an impregnation method and characterized by using advanced techniques. Among the bimetallic catalysts, CoCu/γ-Al₂O₃ exhibited the best performance. The findings revealed that owing to the strong synergistic interaction between Cu, Co, and the γ-Al₂O₃ support, the active species in the CoCu/γ-Al₂O₃ catalyst were effectively stabilized, and they significantly enhanced the redox performance and acidity of the catalyst, demonstrating superior catalytic activity and sulfur resistance. Conversely, the CoFe/γ-Al₂O₃ catalyst performed poorly, exhibiting a significant decline in its activity owing to sulfur poisoning. The insights from this study provide theoretical support for designing efficient, sulfur-resistant catalysts that are crucial to reducing industrial VOC emissions. Full article

The modification of catalytic activity through the use of metallic promoters is a key strategy for optimizing performance, as electronic factors play a crucial role in regulating catalytic behavior. This study explores the electronic factors behind the adsorption of glycerol (Gly) on bimetallic nickel-based compounds (${\mathrm{Ni}}_3\mathrm{X}$) using density functional theory (DFT) calculations; incorporating Mn, Fe, Co, Cu, and Zn as promoters effectively tunes the d-band center of these systems, directly influencing their magnetic, adsorption, and catalytic properties. A good correlation between the calculated glycerol adsorption energy and the d-band filling of the studied bimetallic surfaces was identified. Interestingly, this correlation can be rationalized using the celebrated Newns–Anderson model based on the calculated d-band fillings and centers of the systems under study. Additionally, the adsorption energies and relative stability of other electro-oxidation intermediates toward dihydroxyacetone (DHA) were calculated. Notably, the ${\mathrm{Ni}}_3\mathrm{Co}$ and ${\mathrm{Ni}}_3\mathrm{Cu}$ systems exhibit an optimal balance between glycerol adsorption and DHA desorption, making them promising candidates for glycerol electro-oxidation. These theoretical insights address fundamental aspects of developing glycerol valorization processes and advancing alcohol electro-oxidation technologies in fuel cells with noble-metal-free catalysts. Full article

In this work, combined experimental and modeling techniques were used to understand the bimetallic catalyst formation of Cu and Fe. The first part of this study aims to address this gap by employing analytical techniques such as X-ray diffraction (XRD), thermal and gravimetric (TGA), thermoprogrammed oxidation and reduction. These were used to track the evolution of the different crystalline phases formed for CuFe-Bulk and CuFe/Al₂O₃ catalysts, as well as hydrogen thermoprogrammed reduction (H₂-TPR), to evaluate the reducibility of the oxide phases. Both bulk and supported catalysts were also studied in the hydrogenation of furfural at 170 °C, and 4 MPa of H₂. The research provides insights into the thermal events and structural transformations that occur during oxidation and reduction processes, revealing the formation of multiple oxide and metallic phases. The proposed reaction mechanism obtained from XRD analysis and TG-based mathematical modeling provides valuable information about the chemical reaction and the diffusion control mechanisms. Furthermore, a catalytic test using furfural, a biomass-derived molecule, was conducted. This interconnects with the initial section of the study, in which we found that active Cu₄Fe sites have superior performance in the CuFe/Al₂O₃ catalyst in the hydrogenation batch test. Full article

Zeolites with different structures (P1, sodalite, and X) were synthesized from coal fly ash by applying ultrasonically assisted hydrothermal and fusion–hydrothermal synthesis. Bimetallic catalysts, containing 5 wt.% Ni and 2.5 wt.% Cu, supported on the zeolites, were prepared by a post-synthesis incipient wetness impregnation method. The catalysts were characterized by X-ray powder diffraction (XRPD), N₂ physisorption, transmission electron microscopy (TEM), Mössbauer and X-ray photoelectron spectroscopies (XPS), and H₂–temperature-programmed reduction (H₂-TPR) analyses. The XRPD results showed that crystalline Cu⁰ and Ni_xCu_y intermetallic nanoparticles were formed in the reduced catalysts. The presence of the intermetallic phase affected the reducibility of the nickel by shifting it to a lower temperature, as confirmed by the H₂-TPR curves. Based on the Mössbauer spectroscopic results, it was established that the iron contamination of the coal fly ash zeolites (CFAZs) was distributed in ionic positions of the zeolite lattice and as a finely dispersed iron oxide phase on the external surface of the supports. The formation of the NiFe alloy, not detectable by XRPD, was also evidenced on the impregnated samples. The catalysts were studied in the upgrading of levulinic acid (LA), derived from lignocellulosic biomass, to γ-valerolactone (GVL), in a batch reactor under 30 bar H₂ pressure at 150 and 200 °C, applying water as a solvent. The NiCu/SOD and NiCu/X catalysts showed total LA conversion and a high GVL yield (>75%) at a reaction temperature of 200 °C. It was found that the textural parameters of the catalysts have less influence on the catalytic activity, but rather the stable dispersion of metals during the reaction. The characterization of the spent catalyst found the rearrangement of the support structure. The high LA conversion and GVL yield can be attributed to the weak acidic character of the support and the moderate hydrogenation activity of the Ni-Cu sites with high dispersion. Full article

Cu-based zeolite catalysts face the challenge of high N₂O emissions, while Fe-based zeolite ones suffer from insufficient low-temperature activity and hydrothermal stability. To combat these issues, we developed Cu-Fe-coupled UZM-35 zeolite catalysts with NO_x conversion over 85% in the temperature range of 175 °C. Meanwhile, over 80% of NO_x can be converted between 150 and 550 °C. Furthermore, over 95% of N₂ selectivity was obtained in the whole temperature range. Over these catalysts, Cu and Fe species were uniformly dispersed, being mostly in ionic forms; their presence hardly changed the framework and pore structure of the zeolite. Moreover, the Cu-Fe bimetallic zeolite contained abundant acid sites and even more active species, which ensured its superior catalytic performance for NO_x reduction. In addition, the coupling of Cu and Fe stabilized both framework and active sites; therefore, superior hydrothermal stability was obtained. This study provides valuable insights for the development of SCR catalysts for diesel vehicles aimed at meeting future emission standards. Full article

Metal air batteries have gradually attracted public attention due to their advantages such as high power density, high energy density, high energy conversion efficiency, and clean and green products. Reasonable design of oxygen reduction reaction (ORR) catalysts with high cost-effectiveness, high activity, and high stability is of great significance. Metal organic frameworks (MOFs) have the advantages of large specific surface area, high porosity, and designability, which make them widely used in many fields, especially in catalysis. This paper starts with regulating and optimizing the composition and structure of MOFs. A series of N, S co-doped electrocatalysts FeCuS-N-C were prepared by two high-temperature pyrolysis processes using N-doped carbon hollow nanorods derived from ZIF-8 as the substrate. The one-dimensional nanorod material derived from this MOF exhibits excellent electrocatalytic ORR performance (Eonset = 0.998 V, E_1/2 = 0.874 V). When used as the air cathode catalyst for zinc air batteries and assembled into liquid ZABs, the battery discharge curve was calculated and found to have a maximum power density of 142.7 mW cm⁻², a specific capacity of 817.1 mAh gZn⁻¹, and a cycling stability test of over 400 h. This study provides an innovative approach for designing and optimizing non-precious metal catalysts for zinc air batteries. Full article

Fe/Cu bimetallic catalysts have a synergistic effect that can effectively enhance catalytic activity, so Fe/Cu bimetallic catalysts have been extensively studied. However, the efficacy and mechanisms of Fe/Cu bimetallic catalysts’ peroxidation activation have rarely been explored. In this study, Fe/Cu bimetallic materials were fabricated to catalyze different oxidizing agents, including peroxymonosulfate (PMS), peroxydisulfate (PDS), peroxyacetic acid (PAA), and hydrogen peroxide (H₂O₂), for the degradation of sulfamethoxazole (SMX). The Fe/Cu/oxidant systems exhibited an excellent degradation efficiency of sulfamethoxazole (SMX). In the Fe/Cu/PMS, Fe/Cu/PDS, and Fe/Cu/PAA systems, the main reactive oxygen species (ROS) responsible for SMX degradation were hydroxyl radical (^•OH) and singlet oxygen (¹O₂), while the main ROS was only ^•OH in the H₂O₂ system. The differences in the surface structure of the materials before and after oxidation were examined, revealing the presence of a large amount of flocculent material on the surface of the oxidized PMS material. Anion experiments and actual body experiments also revealed that the PMS system had a strong anti-interference ability. Finally, a comprehensive comparison concluded that the PMS system was the optimal system among the four oxidation systems. Overall, this work revealed that the PMS oxidant has a better catalytic degradation of SMX compared to other oxidizers for Fe/Cu, that PMS generates more ROS, and that the PMS system has a stronger resistance to interference. Full article

The aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) plays a pivotal role in the synthesis of renewable, biodegradable plastics and sustainable chemicals. Although supported gold nanoclusters (NCs) exhibit significant potential in this process, they often suffer from low selectivity. To address this challenge, a series of gold-M (M means Ni, Fe, Cu, and Pd) bimetallic NCs catalysts were designed and synthesized to facilitate the selective oxidation of HMF to FDCA. Our findings indicate that the introduction of doped metals, particularly Ni and Pd, not only improves the reaction rates for HMF tandem oxidation but also promotes high yields of FDCA. Various characterizations techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), in situ diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption (CO-DRIFTS), and temperature-programmed desorption of oxygen (O₂-TPD), were employed to scrutinize the structural and electronic properties of the prepared catalysts. Notably, an electronic effect was observed across the Au-based bimetallic catalysts, facilitating the activation of reactant molecules and enhancing the catalytic performance. This study provides valuable insights into the alloy effects, aiding in the development of highly efficient Au-based bimetallic catalysts for biomass conversions. Full article

In this paper, a detailed mechanism is discussed for two processes: deNOx and deN₂O. An FAU catalyst was used for the reaction with Cu-Fe bimetallic adsorbates represented by a dimer with bridged oxygen. Partial hydration of the metal centres in the dimer was considered. Ab initio calculations based on the density functional theory were used. The electron parameters of the structures obtained were also analysed. Visualisation of the orbitals of selected structures and their interpretations are presented. The presented research allowed a closer look at the mechanisms of processes that are very common in the automotive and chemical industries. Based on theoretical modelling, it was possible to propose the most efficient catalyst that could find potential application in industry–this is the FAU catalyst with a Cu-O-Fe bimetallic dimer with a hydrated copper centre. The essential result of our research is the improvement in the energetics of the reaction mechanism by the presence of an OH group, which will influence the way NO and NH₃ molecules react with each other in the deNOx process depending on the industrial conditions of the process. Our theoretical results suggest also how to proceed with the dosage of NO and N₂O during the industrial process to increase the desired reaction effect. Full article

The qualitative impact of pollutants on water quality is mainly related to their nature and their concentration, but in any case, they determine a strong impact on the involved ecosystems. In particular, refractory organic compounds represent a critical challenge, and several degradation processes have been studied and developed for their removal. Among them, heterogeneous Fenton treatment is a promising technology for wastewater and liquid waste remediation. Here, we have developed mono- and bimetallic formulations based on Co, Cu, Fe, and Mn, which were investigated for the degradation of three model organic dyes (methylene blue, rhodamine B, and malachite green). The treated samples were then analyzed by means of UV-vis spectrophotometry techniques. Bimetallic iron-based materials achieved almost complete degradation of all three model molecules in very short time. The Mn-Fe catalyst resulted in the best formulation with an almost complete degradation of methylene blue and malachite green at pH 5 in 5 min and of rhodamine B at pH 3 in 30 min. The results suggest that these formulations can be applied for the treatment of a broad range of liquid wastes comprising complex and variable organic pollutants. The investigated catalysts are extremely promising when compared to other systems reported in the literature. Full article

This study investigates the potential of bimetallic alloy catalysts, specifically Ni₉₉Pt₁, Cu₉₉Ni₁, Cu₉₉Fe₁, Fe₉₉Pt₁, and Fe₉₉Pd₁, for the synthesis of isobutanol via the Guerbet route. The catalysts were synthesized with a doping of 1 at% Ni, Fe, Pt, and Pd in the base metals Fe, Cu, and Ni. The catalytic properties of these bimetallic alloy catalysts were explored for their potential for promoting the Guerbet reaction. The study aims to test the usability of the theoretically predicted d-band values in the synthesized bimetallic catalysts, which were prepared by means of incipient wetness impregnation, and shows that doping amounts smaller than 1 at% already significantly improved the catalytic activity of the base metals. In particular, the doping of nickel with platinum yielded an effective catalyst for the synthesis of isobutanol via the Guerbet pathway. The Ni₉₉Pt₁/C catalyst from the presented experiments had the highest Space Time Yield (STY) and is, therefore, also a promising catalyst for the hydrogen-borrowing reactions class. Full article

The effluent discharged from wastewater treatment facilities frequently enters the ocean, posing a considerable threat to the health of marine life and humans. In this paper, an alkali lignin-based biochar-loaded modified Fe–Cu catalyst (FeCu@BC) was prepared to remove soluble microbial products (SMP) from secondary effluent as disinfection by-products precursors at ambient temperature and pressure. The humic acid (HA) was taken as the representative substance of SMP. The results showed that the maximum removal efficiency of HA reached 93.2% when the FeCu@BC dosage, pH, initial HA concentration, and dissolved oxygen concentration were 5.0 g/L, 7, 100 mg/L, and 1.75 mg/L, respectively. After three cycles, the removal efficiency of HA could be maintained at more than 70%. The quenching experiments and electron spin resonance (EPR) results showed that •OH and ¹O₂ were involved in the degradation of HA in the FeCu@BC catalyst reaction system, with ¹O₂ playing a dominant role. Theoretical calculations confirmed that •OH and ¹O₂ were more prone to attack the C=O bond of the side chain of HA. After processing by the FeCu@BC catalyst, the yield of chlorinated disinfection by-products from secondary effluent had decreased in an obvious manner. This study provides a new solution to efficiently solve the problem of chlorinated disinfection by-products from HA. Full article

This research explores the enhancement of bio-oil quality through upgrading with the magnetic bimetallic oxide (CuO-Fe₃O₄) catalysts supported on activated rice straw biochar (AcB). These catalysts were employed in a supercritical ethanol-based upgrading process. Various characterization techniques, including elemental analysis, Fourier transform infrared (FTIR), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM), were utilized to characterize the prepared catalysts. This study revealed significant improvements in the physical characteristics and chemical composition of the bio-oil, with an increase in the heating value (HHV) from 21.3 to 32.1 MJ/kg. Esterification and transesterification were identified as key reactions contributing to this improvement. Notably, the pH of bio-oil increased from 4.3 (raw bio-oil) to 5.63 (after upgrading), signifying reduced acidity. The analysis of the bio-oil’s chemical composition highlighted a decrease in oxygen content and an increase in carbon and hydrogen content. At the optimum conditions, the application of supercritical ethanol proved to be an efficient method for enhancing the bio-oil’s properties. A crucial transformation occurred during the upgrading process and more than 90% of carboxylic acids were converted into esters, primarily ethyl acetate at the optimal conditions. This study has demonstrated the effective enhancement of raw bio-oil from rice straw through the utilization of carbon-based bimetallic oxide catalysts in a supercritical upgrading procedure. Full article