Catalyst For Synthesis Research Articles

Iron-based graphene composite for oxygen reduction reaction in alkaline media: Electrocatalytic activity and lifetime evaluation

The development of electrocatalysts with high catalytic performance and low costs for oxygen reduction reaction (ORR) is still challenging. Herein, an overall solution for ORR in alkaline media, from the catalyst synthesis to catalyst regeneration and to the development of a rapid, reliable and easy approach for electrode surface evaluation, is presented. We focused on the development and characterization of an efficient material for ORR in alkaline media, α-Fe2O3 N-doped graphene (Fe-N-Gr). The associative pathway for the four electron transfer ORR mechanism is sustained by the Raman spectra recorded from the electrode surface. We highlighted the possibility of catalyst regeneration by a simple electrochemical method. After two regeneration rounds and 1500 cycles in O2-saturated 1 M NaOH, the catalyst still retains 40.8 % catalytic activity. Finally, as a part of the overall solution, we demonstrated that a methodology based on Raman spectroscopic measurements and machine learning algorithms can be applied for graphene-based catalysts lifetime investigation.

Efficient Electrocatalytic Ammonia Synthesis via Theoretical Screening of Titanate Nanosheet-Supported Single-Atom Catalysts

The electrocatalytic nitrogen reduction reaction (NRR) for synthesizing ammonia holds promise as an alternative to the traditional high-energy-consuming Haber–Bosch method. Rational and accurate catalyst design is needed to overcome the challenge of activating N2 and to suppress the competitive hydrogen evolution reaction (HER). Single-atom catalysts have garnered widespread attention due to their 100% atom utilization efficiency and unique catalytic performance. In this context, we constructed theoretical models of metal single-atom catalysts supported on titanate nanosheets (M-TiNS). Initially, density functional theory (DFT) was employed to screen 12 single-atom catalysts for NRR- and HER-related barriers, leading to the identification of the theoretically optimal NRR catalyst, Ru-TiNS. Subsequently, experimental synthesis of the Ru-TiNS single-atom catalyst was successfully achieved, exhibiting excellent performance in catalyzing NRR, with the highest NH3 yield rate reaching 15.19 μmol mgcat−1 h−1 and a Faradaic efficiency (FE) of 15.3%. The combination of experimental results and theoretical calculations demonstrated the efficient catalytic ability of Ru sites, validating the effectiveness of the constructed theoretical screening process and providing a theoretical foundation for the design of efficient NRR catalysts.

Synthesis of chiral Cu(II) complexes from pro-chiral Schiff base ligand and investigation of their catalytic activity in the asymmetric synthesis of 1,2,3-triazoles

A pro-chiral Schiff base ligand (HL) was synthesized by the reaction of 2-amino-2-ethyl-1,3-propanediol and pyridine-2-carbaldehyde in methanol. The reaction of HL with CuCl2·2H2O and CuBr2 in methanol gave neutral mononuclear Cu(II) complexes with general formula of [Cu(HL)Cl2] (1) and [Cu(HL)Br2] (2), respectively. By slow evaporation of the methanolic solutions of 1 and 2, their enantiomers were isolated in crystalline format. The formation of pure chiral crystals in the racemic mixture was amply authenticated by single crystal X-ray analysis, which indicated that S-[Cu(HL)Cl2], R-[Cu(HL)Cl2], and S-[Cu(HL)Br2] are crystallized in chiral P212121 space group of orthorhombic system. Preferential crystallization was used to isolate the R and S enantiomers as single crystals and the isolated compounds were also studied by CD analysis. Structural studies indicated that the origin of the chirality in these compounds is related to the coordination mode of the employed pro-chiral ligand (HL) because one of its carbon atoms has been converted to a chiral center in the synthesized complexes. Subsequently, these complexes were used in click synthesis of a β-hydroxy-1,2,3-triazole and the results of catalytic studies indicated that 1 and 2 can act as enantioselective catalysts for the asymmetric synthesis of β-hydroxy-1,2,3-triazole product under mild condition. This study illustrates the significant capacity of the use of pro-chiral ligands in preparing chiral catalysts based on complexes which can also be considered as an effective approach to cheap chiral catalysts from achiral reagents.

Regulating the electronic property of iron catalysts for higher alcohols synthesis from CO2 hydrogenation

The electronic property of a catalyst is crucial to the generation of key reaction intermediates for targeted synthesis. Herein, we reported a strategy by modifying iron catalysts with sulfate and alkali metal (Li, Na, or K) to regulate the electronic property and optimize the reaction pathways for CO2 hydrogenation to higher alcohols. The characterizations demonstrated the influencing relationship between the electronic property of iron catalysts and the catalytic capabilities for CO dissociation, non-dissociated CO activation and catalytic hydrogenation, which were critical to selective synthesis of higher alcohols. Na-S modification was proven more effective to balance the multiple capabilities required for higher alcohols synthesis and the NaS-Fe catalyst gave a higher C2+OH yield in CO2 hydrogenation. DFT calculations further validated the advantage of Na-S modification from the aspects of CO adsorption and C−C coupling. This strategy provides more flexibility in site regulation and applies to catalyst design for many reactions.

Machine Learning-Assisted Study of RENxC6-x-Doped Graphene as Potential Electrocatalysts for Oxygen Electrode Reactions.

In the application of renewable energy, the oxidation-reduction reaction (ORR) and oxygen evolution reaction (OER) are two crucial reactions. Single-atom catalysts (SACs) based on metal-doped graphene have been widely employed due to their high activity and high atom utilization efficiency. However, the catalytic activity is significantly influenced by different metals and local coordination, making it challenging to efficiently screen through either experimental or density functional theory (DFT) calculations. To address this issue, this study employed a combination of DFT calculations and machine learning (DFT-ML) to investigate rare earth-modified carbon-based (RENxC6-x) electrocatalysts. Based on computational data from 75 catalysts, we trained two ML models to capture the underlying patterns of physical properties and overpotential. Subsequently, the candidate catalysts were screened, leading to the discovery of four ORR catalysts, nine OER catalysts, and five bifunctional electrocatalysts, all of which were thoroughly validated for their stability. Lastly, by integrating the ML models with the SHAP analysis framework, we revealed the influence of atomic radius, Pauling electronegativity, and other features on the catalytic activity. Additionally, we analyzed the physicochemical properties of potential catalysts through DFT calculations. The revolutionary DFT-ML approach provides a crucial driving force for the design and synthesis of potential catalysts in subsequent studies.

Fabrication and characterization of copper complex immobilized on magnetic nanoparticles: an efficient and ecofriendly nanomagnetic catalyst for synthesis of imidazo[1,2-a]pyridines and pyranopyrazoles

Fabrication and characterization of copper complex immobilized on magnetic nanoparticles: an efficient and ecofriendly nanomagnetic catalyst for synthesis of imidazo[1,2-a]pyridines and pyranopyrazoles

Cu(I)‐Catalyzed Coupling Reactions of β‐Nitrostyrene, 1,3‐Dicarbonyl compound & Aryl amine: An Efficient Method For the Synthesis of Polysubstituted Pyrroles

AbstractA convenient Cu(I) Catalyzed three‐component coupling strategy for the synthesis of polysubstituted pyrroles is developed using simple and readily available building blocks like, 1, 3‐dicarbonyl compound, aryl amine, and β‐nitrostyrene. CuI has been rarely explored for the pyrrole ring synthesis and a comparative analysis of our current catalyst with a range of previously reported catalysts suggested that, CuI is one of the best catalysts for the multicomponent synthesis of polysubstituted pyrrole derivatives. Notably, this process has several advantages, including a simple and practical set‐up with hassle free reaction conditions, extensive substrate scope, short reaction time, high atom economy and environmentally favorable approach. This methodology provides an alternative approach to the highly substituted pyrroles and under optimized reaction conditions, polysubstituted pyrroles were formed in good to excellent yields. Cu(I) catalyzed Mannich reactions followed by Michael addition reactions along with subsequent intramolecular cyclization are believed to be the key steps of this reaction process.

Effect of poling on photocatalytic activity with SrBi4Ti4O15 catalyst

Effect of poling on photocatalytic activity with SrBi₄Ti₄O₁₅ catalyst

Effect of a novel metal-free green synthesis catalyst on the positive role of microwave irradiation in hydrogen production from the hydrolysis of sodium borohydride

This study demonstrates the synthesis of hydrochar, a high-value material, from watermelon seed husk, a low-value waste material, using the hydrothermal synthesis method. The microwave power effect plays an important role in the use of metal-free and environmentally friendly catalysts for the hydrolysis of sodium borohydride. The XRD, BET, SEM, and FTIR analyses characterized the catalyst. X-ray diffraction revealed the catalyst structure to be cellulosic. The surface area and total pore volume were 1.063 m2/g and 0.0195 cm3/g, respectively, in BET analysis. According to the IUPAC classification, the catalyst conformed to the type III isotherm. This study investigated how good the catalyst for the hydrolysis of sodium borohydride was when it was exposed to microwave irradiation at different microwave powers, solution temperatures, and catalyst amounts. The Langmuir-Hinshelwood and nth-order kinetic models calculated the activation energies to be 82.192 and 83.35 kJ/mol, respectively. The use of bio-waste hydrochar as a catalyst in the hydrolysis of sodium borohydride in the microwave environment shows promising results in the search for metal-free catalysts.

Waste snail shells-derived mixed oxide catalyst for efficient transesterification of vegetable oil: Towards sustainable biodiesel production

This study explores the transesterification process of soybean oil for the production of biodiesel, utilizing an innovative mixed oxide catalyst obtained from discarded snail shells powder. The catalyst synthesis involved a thermal treatment at 900°C for 120 min, predominantly yielding calcium oxide (CaO). In order to evaluate its properties, we carried out a thorough characterization using various analytical techniques. The study explores the impact of crucial variables on the transesterification reaction, such as reaction time (from 30 to 150 min), methanol-to-oil ratio (from 3:1–18:1), and catalyst concentration (from 0.5% to 4% by weight). Optimal conditions emerged with a 90-min reaction time, a 12:1 methanol-to-oil ratio, and a 2% catalyst loading, yielding an impressive biodiesel conversion rate of approximately 93%. The validity of biodiesel conversion was confirmed through Fourier transform infrared spectroscopy (FTIR) and Proton Nuclear Magnetic Resonance Spectroscopy (1 H NMR). The resultant biodiesel exhibited highly favorable characteristics, including an acid value of 0.85 mg of KOH/g, a density of 886.8 kg/m3, and a viscosity of 4.6 mm2/s. These measurements align with the standards set forth in EN 14214 and ASTM D6751 regarding biodiesel quality. The utilization of waste snail shells powder as a precursor for synthesizing the mixed oxide catalyst presents a promising approach for the sustainable production of biodiesel from soybean oil, offering a sustainable and efficient approach to biofuel production.

Catalytic pyrolysis of wood dust for monophenol over macroalgal biochar-based catalyst: Effects of activation agents and atmospheres during catalyst synthesis on its performance

After introducing heteroatoms into the carbon material skeleton, the performance of carbocatalyst during catalytic pyrolysis of biomass for monophenol production is significantly improved. Algae, as a carbon source with intrinsic nitrogen content, is well-identified as a suitable raw material for preparing heteroatom-doped carbocatalyst. The present study aimed to investigate the effects of different alkaline activation agents (KOH/NaOH) and gas atmospheres (N2/CO2) during the carbonization-activation synthesis process of macroalgal biochar-based catalysts (MBBCs) on their properties and performances. Characterizations of carbocatalysts were carried out via BET and XPS analyses to investigate the porous structures and surface functional groups. Results showed that CO2, as a weakly oxidizing atmosphere, can promote the formation of porous structure of MBBCs. However, the promotion is not as strong as that of chemical activation agents (KOH/NaOH). Furthermore, KOH can promote the formation of porous structure more strongly than NaOH, but NaOH can substantially enhance the formation of surface oxygen‑nitrogen groups compared to KOH. All the MBBCs exhibited the increment of monophenols in the bio-oil obtained from catalytic pyrolysis of wood dust, especially phenol, o-cresol, and p-cresol. Amongst, the biochar-based catalyst activated with NaOH in CO2 atmosphere was the most effective one in promoting monophenols content (up to 59.46 %). Compared with the control group (without catalyst), the phenol content was increased from 5.03 % to 19.40 %. Moreover, it is found that the catalytic performance was positively correlated with the CO species percentage on the surface of MBBCs. The macroalgal biochar-based catalyst has an excellent catalytic performance, which is of great significance for achieving the complete utilization of algae and thereby improving the quality of catalytic pyrolysis products.

The regulatory role of cysteine in active phase construction of polyoxometalate-based hydrodesulfurization catalysts: Reduction, chelation, and dispersion

Polyoxometalate-based hydrodesulfurization (HDS) catalysts were modified using cysteine to construct efficient CoMoS active phase. Cysteine, characterized by chelating (–COOH, –NH2) and reducing (−SH) groups, assumed a triple role in catalyst synthesis, including reduction, chelation, and dispersion. Cysteine pre-reduced polyoxometalates to heteropoly blue, significantly increasing the catalyst sulfidation. The increased nucleophilicity of heteropoly blue enhanced their attraction to Co2+ ions, intensifying the Co-Mo bimetallic synergy. The formation of Co-chelate species delayed Co sulfidation, allowing for the concurrent sulfidation of both Co and Mo species and promoting the generation of the CoMoS active phase. Carbonaceous deposits from the high-temperature carbonization of cysteine weakened the metal-support interaction, facilitating the dispersion of the active phase. The S-CoPMo12-Cys/Al2O3 catalyst demonstrated high activity in the HDS reaction of dibenzothiophene, showcasing their potential for advanced HDS reaction.

The Pd/ZrO2 catalyst inversely loaded with various metal oxides for methanol synthesis from carbon dioxide

The selectivity and stability of catalysts for methanol synthesis from CO2 still remain to be enhanced. In this work, we synthesized a series of Pd/ZrO2 catalysts inversely loaded with various metal oxide promoters (ZnO, In2O3, and CeO2), those would partially cover Pd metal surface and form some new metal-promoter interface, to explore the nature in the performance of CO2 hydrogenation to methanol. The catalyst synthesized by this approach could limit the growth of Pd particles during the reduction and form new metal–metal oxide interfaces with different functions of CO2 hydrogenation, improving the reaction performance of Pd-ZrO2 catalysts. As a result, the ZnO-Pd/ZrO2 catalyst exhibited the highest CO2 conversion (12.0 %), methanol selectivity (95.6 %), and STY of methanol (472 gMeOHkgcat-1h−1), with excellent stability. The results of HRTEM, H2-TPR, XPS, and XAFS showed that the ZnO-Pd/ZrO2 catalyst had the typical Pd-ZnO interface with Pd2+ species after the H2 reduction, which could enhance the adsorption and activation of CO2. In addition, the in situ DRIFTS and NAP-XPS results implied that the Pd-ZnO interface significantly improved the formation of formate (HCOO*) and methoxy (H3CO*) species, which were considered to be the key intermediates of methanol generation, and thus greatly enhanced the selectivity of methanol.

Amorphous Bismuth-Tin Oxide Nanosheets with Optimized C-N Coupling for Efficient Urea Synthesis.

Closing the carbon and nitrogen cycles by electrochemical methods using renewable energy to convert abundant or harmful feedstocks into high-value C- or N-containing chemicals has the potential to transform the global energy landscape. However, efficient conversion avenues have to date been mostly realized for the independent reduction of CO2 or NO3-. The synthesis of more complex C-N compounds still suffers from low conversion efficiency due to the inability to find effective catalysts. To this end, here we present amorphous bismuth-tin oxide nanosheets, which effectively reduce the energy barrier of the catalytic reaction, facilitating efficient and highly selective urea production. With enhanced CO2 adsorption and activation on the catalyst, a C-N coupling pathway based on *CO2 rather than traditional *CO is realized. The optimized orbital symmetry of the C- (*CO2) and N-containing (*NO2) intermediates promotes a significant increase in the Faraday efficiency of urea production to an outstanding value of 78.36% at -0.4 V vs RHE. In parallel, the nitrogen and carbon selectivity for urea formation is also enhanced to 90.41% and 95.39%, respectively. The present results and insights provide a valuable reference for the further development of new catalysts for efficient synthesis of high-value C-N compounds from CO2.

Synthesis and density functional theory study of functionalized Oxazolidine-2-ones using a novel MnFe2O4@SiO2-SiO3H magnetic nanocatalyst

This study introduces MnFe2O4@SiO2-SiO3H as a novel magnetic catalyst and thoroughly investigates its structure, catalytic activity, and reusability. The synthesis of the magnetic catalyst was meticulously characterized using an array of analytical techniques. Utilizing MnFe2O4@SiO2-SiO3H, the synthesis of functionalized oxazolidine-2-ones were performed, versatile compounds widely employed in chiral auxiliaries, protecting groups, and medicinal chemistry. Remarkably, the two-step process from chalcones demonstrated one of the shortest reported pathways, highlighting the efficiency of our novel nanocatalyst. To elucidate the stability and reactivity of the synthesized products, we employed Density Functional Theory (DFT) calculations, including molecular electrostatic potential (MEP) mapping and reactivity indices such as electronegativity, electrophilic index, softness, and hardness, as well as frontier molecular orbitals (HOMO-LUMO). Furthermore, our investigations extended to the recycling capabilities of the nanocatalyst. Through a comprehensive evaluation of at least five reaction cycles, MnFe2O4@SiO2-SiO3H showcased a remarkable retention of activity (97–92 %), reaffirming its reusability and long-term potential. Our research presents MnFe2O4@SiO2-SiO3H as a highly effective and recoverable nanomagnetic catalyst for organic reactions, with demonstrated applications in synthesizing functionalized oxazolidine-2-ones. As such, our findings offer a promising alternative to traditional methods, presenting new opportunities in catalysis and materials science.

Modulating band structure of g-C3N4 by doping oxygen to transform FeCo2O4/g-C3N4 heterojunction from type-II to S-scheme for enhancing photo-Fenton-like reaction

Constructing S-scheme heterojunctions is a highly prevalent approach in enhancing the activation efficiency of peroxymonosulfate (PMS). However, the two semiconductors that have the potential to form S-scheme heterojunction (such as FeCo2O4 and carbon nitride) typically tend to form type-II heterojunction. In this study, through oxalic acid assisted oxygen atom doping in carbon nitride, followed by the utilization of oxygen-doped carbon nitride (O-CN) as precursors in combination with cobalt chloride and iron chloride, the final synthesis of a novel composite catalyst is achieved. The introduction of oxygen atoms into the graphite carbon nitride can lead to an overall reduction in the band structure, facilitating the controlled transformation of a type-II heterojunction to an S-scheme heterojunction. This transformation is confirmed through density functional theory (DFT) calculations and electron spin resonance (ESR) tests. In the photo-Fenton-like system, the 15% FeCo2O4/Oxygen doped-C3N4 (FCOCN) catalyst demonstrated a remarkable degradation efficiency of 93.5% for tetracycline hydrochloride (TCH). This efficiency surpassed that of O-CN (47.8%) and FeCo2O4 (60.3%). Furthermore, the degradation efficiency of the 15% FCOCN catalyst was significantly higher than that of photocatalysis (2.04 times greater) and Fenton-like treatment (1.11 times greater). Remarkably, within a short period of 14min, the emerging contaminants, including sulfamethoxazole (SMX), bisphenol A (BPA), and carbamazepine (CBZ), were completely degraded. Atrazine (ATZ) showed a remarkable degradation rate of 77.1%. This study offers valuable insights into the construction of S-scheme heterojunction through the manipulation of band structure in type-II heterojunction by oxygen doping.

Synthesis of biomass nitrogen-doped catalysts and their electrocatalytic performance in fuel cells

At present, biomass materials have the characteristics of low cost, stability, and relatively high activity, which is expected to replace platinum-based (Pt) materials as cathode catalysts. In this paper, Zn, Fe-N-C catalyst materials and Fe-N-C catalyst were composited by high-temperature calcination. Their crystal and morphological structures were featured by X-ray diffraction instruments (XRD) and scanning electron microscopy (SEM). Their activity and stability to oxygen reduction were tested by an electrochemical workstation, and it was found that Zn, Fe-N-C catalyst materials had the best performance. The investigation of this paper can furnish an effective method for oxygen reduction reaction catalysts.

Effect of the Nitrogen/Carbon Ratio in the Organic Ligand of a Nickel Single-Atom Catalyst on its Electrochemical Activity in CO2 Reduction

Simple, large-scale synthesis of metal single-atom catalysts (SACs) is limited by the aggregation of metal atoms on the support material surface. The N atoms in small organic ligands (SOLs) can anchor single metal atoms, affording abundant surface-active sites. In this study, we investigated the effect of the nitrogen/carbon ratio (N/C) in SOLs on the properties of the resultant Ni single-atom confined nitrogen-doped carbon black (Ni-NCB). The N/C ratio affected the thermal stability of Ni-NCB_N/Cs during carbonization, and the optimal Ni-NCB (Ni-NCB_0.5) was synthesized with the SOL 2-methylimidazole. Ni-NCB_0.5 achieved a CO partial current density of > 500mAcm–2 and high CO Faradaic efficiency (96.4%) in the CO2 reduction reaction. The 3- and 4-cell stack systems with Ni-NCB_0.5 (25 cm2 area per unit cell) exhibited an overall current of 10A, high CO selectivity (> 96.0%), and long-term stability (50h). This synthetic strategy for SACs can be commercialized and even extended to other industrial electrocatalysts.

One pot green synthesis of Biginelli reaction catalysed by bio-waste metal-free super acid lignin sulphonate

A Bio-waste metal-free super acid catalyst (BWC) has been synthesized at higher temperature and used as a catalyst for synthesis of 3,4-dihydropyrimidine-2-(1H)-ones (DHPMs) via one pot three component Biginelli reaction. The multicomponent reactions are very complex and involves more than two reagents. In the present study, sulfonated carbonaceous material called a green catalyst was utilized for three component reaction. Catalyst was synthesized from sodium lignosulfonate which is obtained from the wastage of paper-making industries from the sulfite pulping process. The synthesized green catalyst was characterized by FT-IR, Thermal Gravimetric Analysis (TGA) scanning electron microscopy (SEM), Thermal Electronic microscopy (TEM), and elemental analysis. The three component Biginelli synthesis the catalyst was optimized to 8 mol % quantity which was sufficient to complete the reaction within 1–4 hrs. The yield of reaction ranges from 70-90 %. Separation was easy and recycling ability of catalyst was also tested with good retention of catalytical activity. Catalytic activity was performed as an acid-catalyzed reaction in ethanol. The synthesis of all the compounds were confirmed by 1H NMR (Nuclear magnetic resonance), MS (Mass Spectra), FT-IR (Fourier Transform Infrared), CHNS (Carbo, Hydrogen, Nitrogen, Sulphur) analysis. The satisfactory results were obtained with good yields, shorter reaction time and simplicity in the experimental procedure. The catalysts could be recycled and reused three times without decrease in the catalytic activity significantly.

Mild activation of spent fluid catalytic cracking (FCC) catalysts for the pilot synthesis of zeolite a with commercial quality and excellent Co2+ removal ability

Fluid catalytic cracking (FCC) plays a pivotal role in the transformation of crude oil into fuels and bulk chemicals, crucial within petroleum refining. However, it also generates a substantial volume of hazardous spent FCC catalysts. Thus, developing an effective method to convert these hazardous spent catalysts into high-value products is essential for the sustainable advancement of the petrochemical industry. In this study, we introduce a simple, mild, and environmentally friendly activation approach for spent FCC catalysts, followed by a straightforward synthesis of zeolite A meeting commercial standards. The resulting zeolite A (referred to as SFCC-A) exhibited high crystallinity, exceptional selectivity, and efficient Co2+ removal capabilities from wastewater. Even at a solid/liquid ratio of 1/1000 g·mL−1, a removal efficiency of approximately 99 % was achieved. SFCC-A demonstrated a high adsorption capacity (180.5 mg·g−1) for Co2+ and a broad operational pH range (4–8). Furthermore, the pilot synthesis was successfully scaled up to 100 L, maintaining consistent product performance compared to lab-scale production. Additionally, we investigated the evolution of species during the activation of spent FCC catalysts using multiple characterization techniques, elucidated the phase diagram of SFCC-A and the crystallization process under optimal conditions. The combination of a simple, mild, and eco-friendly activation method with a convenient synthesis process, yielding high-value zeolite A products, transforms spent FCC catalysts into valuable resources rather than hazards.