Nanoparticle Catalysts Research Articles

Sustainable Aerobic Transamidation and Esterification of N-Heteroaryl Amides by Heterogeneous Copper Catalyst

Transamidation of secondary amides via heterogeneous strategy has remained an unsolved problem. Here we report a novel and efficient approach for transamidation and esterification of ubiquitous N-heteroaryl amides with various amines and alcohols that exploits an engineered heterogeneous supported copper nanoparticles catalyst. This method overcomes the difficulty of heterogeneous catalysts, which can only achieve transamidation of primary amide driven by the emission of ammonia gas. A broad diversity of N-heteroaryl amides containing quinolin-2-yl, isoquinolin-1-yl, pyrazin-2-yl and pyridin-2-yl directing groups convert into corresponding α-ketoamides and α-ketoesters using needle-shape copper nanoparticles supported on γ-Al2O3 as heterogeneous catalyst. This environmentally benign, catalyst recyclable and easy-to-handle catalysis methodology will have great application prospects in the pharmaceutical synthesis and biological or chemical industry.

The Catalysts-Based Synthetic Approaches to Quinolines: A Review.

The most common heterocyclic aromatic molecule with potential uses in industry and medicine is quinoline. Its chemical formula is C9H7N, and it has a distinctive double-ring structure with a pyridine moiety fused with a benzene ring. Various synthetic approaches synthesize quinoline derivatives. These approaches include solvent-free synthetic approach, mechanochemistry, ultrasonic, photolytic synthetic approach, and microwave and catalytic synthetic approaches. One of the important synthetic approaches is a catalyst-based synthetic approach in which different catalysts are used such as silver-based catalysts, titanium-based nanoparticle catalysts, new iridium catalysts, barium-based catalysts, iron-based catalysts, gold-based catalysts, nickel-based catalyst, some metal-based photocatalyst, α-amylase biocatalyst, by using multifunctional metal-organic framework-metal nanoparticle tandem catalyst etc. In the present study, we summarized different catalyst-promoted reactions that have been reported for the synthesis of quinoline. Hopefully, the study will be helpful for the researchers.

Turning on Low-Temperature Catalytic Conversion of Biomass Derivatives through Teaming Pd1 and Mo1 Single-Atom Sites.

On-purpose atomic scale design of catalytic sites, specifically active and selective at low temperature for a target reaction, is a key challenge. Here, we report teamed Pd1 and Mo1 single-atom sites that exhibit high activity and selectivity for anisole hydrodeoxygenation to benzene at low temperatures, 100-150 °C, where a Pd metal nanoparticle catalyst or a MoO3 nanoparticle catalyst is individually inactive. The catalysts built from Pd1 or Mo1 single-atom sites alone are much less effective, although the catalyst with Pd1 sites shows some activity but low selectivity. Similarly, less dispersed nanoparticle catalysts are much less effective. Computational studies show that the Pd1 and Mo1 single-atom sites activate H2 and anisole, respectively, and their combination triggers the hydrodeoxygenation of anisole in this low-temperature range. The Co3O4 support is inactive for anisole hydrodeoxygenation by itself but participates in the chemistry by transferring H atoms from Pd1 to the Mo1 site. This finding opens an avenue for designing catalysts active for a target reaction channel such as conversion of biomass derivatives at a low temperature where neither metal nor oxide nanoparticles are.

Reactivity and Stability of Reduced Ir-Weight TiO2-Supported Oxygen Evolution Catalysts for Proton Exchange Membrane (PEM) Water Electrolyzer Anodes.

Reducing the iridium demand in Proton Exchange Membrane Water Electrolyzers (PEM WE) is a critical priority for the green hydrogen industry. This study reports the discovery of a TiO2-supported Ir@IrO(OH)x core-shell nanoparticle catalyst with reduced Ir content, which exhibits superior catalytic performance for the electrochemical oxygen evolution reaction (OER) compared to a commercial reference. The TiO2-supported Ir@IrO(OH)x core-shell nanoparticle configuration significantly enhances the OER Ir mass activity from 8 to approximately 150 A gIr-1 at 1.53 VRHE while reducing the iridium packing density from 1.6 to below 0.77 gIr cm-3. These advancements allow for viable anode layer thicknesses with lower Ir loading, reducing iridium utilization at 70% LHV from 0.42 to 0.075 gIr kW-1 compared to commercial IrO2/TiO2. The identification of the Ir@IrO(OH)x/TiO2 OER catalyst resulted from extensive HAADF-EDX microscopic analysis, operando XAS, and online ICP-MS analysis of 30-80 wt % Ir/TiO2 materials. These analyses established correlations among Ir weight loading, electrode electrical conductivity, electrochemical stability, and Ir mass-based OER activity. The activated Ir@IrO(OH)x/TiO2 catalyst-support system demonstrated an exceptionally stable morphology of supported core-shell particles, suggesting strong catalyst-support interactions (CSIs) between nanoparticles and crystalline oxide facets. Operando XAS analysis revealed the reversible evolution of significantly contracted Ir-O bond motifs with enhanced covalent character, conducive to the formation of catalytically active electrophilic OI- ligand species. These findings indicate that atomic Ir surface dissolution generates Ir lattice vacancies, facilitating the emergence of electrophilic OI- species under OER conditions, while CSIs promote the reversible contraction of Ir-O distances, reforming electrophilic OI- and enhancing both catalytic activity and stability.

Hollow silicalite-1 encapsulated nickel nanoparticles as highly stable catalysts in maleic anhydride hydrogenation

Anchoring active metal particles in zeolite cages can significantly improve catalytic stability. In this study, hollow silicalite-1 (HoS-1) encapsulated Ni nanoparticles catalyst (Ni@HoS-1) was prepared using the impregnation method and applied in MA hydrogenation. The encapsulation mechanism was explained as the zeolite wall restricting the evaporation of water in HoS-1, hence Ni particles would be spontaneously enriched within the zeolite cage after drying and calcination. Experiments revealed the specially designed structure effectively protected Ni particles from leaching, and after 5 cycles in liquid-phase batch reactions, the final MA conversion of Ni@HoS-1 is 40.8 % higher than that of Ni/S-1 (85.5 % vs 44.7 %). Moreover, the low acidity of Ni@HoS-1 also delayed the accumulation of carbon deposits, extending the continuous reaction lifespan from 128 h of Ni/S-1 to 188 h. These findings provided a new perspective for the controllable locating of active metal sites against the supports.

Investigation on CuO nanoparticle enhanced mahua biodiesel/diesel fuelled CI engine combustion for improved performance and emission abetted by response surface methodology

In this study, the characteristics of diesel engines were tested with in-house produced mahua biodiesel blended with diesel and copper oxide nanoparticles (CuO NP) catalyst. The preliminary investigation used mahua biodiesel-diesel blends (M10, M20, and M30) among them M20 outperformed. Further M20 and CuO NP with concentrations of 25, 50, and 75 ppm are studied. Finally, the response surface methodology (RSM) was used to determine the appropriate NP concentration for M20. The findings showed that the blend of M20 with 60 ppm NP at 80% load had the highest desirability (0.9740), and the developed RSM model predicted engine responses with a mean absolute percentage error (MAPE) of 3.0962% to the confirmation test confirming the model’s accuracy. The optimized M20NP60 blend demonstrated superior combustion, performance and emission characteristics.

Trace Iron-Modified CeO₂-supported Core-shell CoO@Co Catalyst for Selective Conversion of Furfural to 1,5-Pentanediol.

In the conversion of furfural using non-noble metal catalysts, preferential cleavage of the C2-O bond followed by hydrogenation of the C=C bond facilitates selective access to valuable 1,5-pentanediol (1,5-Ped). Herein, we developed CeO₂ loaded core-shell CoO@Co nanoparticle catalysts. Adjusting Co loading, Fe doping, and reduction temperature improved reaction efficiency. 7Co-0.2Fe/CeO₂ catalysts reduced at 500 °C demonstrated optimal performance. 1,5-Ped produced at 54.76 mmol/g(Co)/h, representing the top activity levels among the reported catalysts. H₂-TPR, XRD, HAADF-STEM, FT-IR, XPS, and XANES were employed to investigate the catalyst structure-activity relationship. Co²⁺ cleaves furan ring C-O bond, Co⁰ promotes double-bond hydrogenation. The CoO@Co structure favors the desired 1,5-Ped production route. Trace Fe species optimize the Co²⁺/Co⁰ ratio, enhance the substrate adsorption, and inhibit the furan ring saturation. These findings emphasize the importance of fine-tuning catalyst structure and composition for selectivity improvement.

Highly stable platinum catalyst encapsulated with mesoporous silica for preferential oxidation of CO in H2-rich stream

Preferential oxidation of CO in H₂-rich streams (PROX) is an effective method to reduce trace amounts of CO for proton exchange membrane fuel cells. However, developing highly stable catalysts for practical reaction conditions achieving the 50:50 goal—below 50 ppm CO concentration with 50% O₂ selectivity—remains challenging. Here, we report a highly stable Pt nanoparticle catalyst encapsulated in mesoporous silica (Pt@mSiO2) loaded on a monolith, which achieves the 50:50 goal. Over 1000 h of continuous PROX reactions in the presence of H2O and CO2, the catalyst maintained an average CO concentration of ca. 33 ppm and O2 selectivity of ca. 50%. The excellent activity, selectivity, and long-term stability of Pt@mSiO₂, which can be attributed to the small size (ca. 2.7 nm) of Pt nanoparticles stably encapsulated in interconnected micro- and meso-porous silica without agglomeration, offer great potential for practical PROX applications.

Catalytic reduction of p-nitrophenol and Eosin Yellow by lemongrass tea-stabilized copper nanoparticles

ABSTRACT Green synthesis of nanoparticles for catalytic applications remains of continued interest, especially for reactions that would occur on an industrial scale or that may be of environmental significance. Here, ultrasmall 2.1-nm copper nanoparticles were synthesized under ambient conditions using a copper sulfate pentahydrate precursor and lemongrass extract as a reducing and capping agent. Their potential to act as catalysts was tested using model reactions: the sodium borohydride reduction reactions of p-nitrophenol and Eosin Yellow. Kinetics measurements were obtained with visible time-course spectroscopy and showed that copper nanoparticles effectively catalyzed both reactions. Temperature dependence followed Arrhenius behavior, indicating the catalyst surface was accessible to reactants. Activation energies of 59.2 and 38.5 kJ/mol were obtained for the reduction reactions of p-nitrophenol and Eosin Yellow, respectively. Large frequency factors for both reactions were found, implying large numbers of catalytic sites and/or facilitation of reaction by capping agents. This copper nanoparticle catalyst prepared via green synthesis demonstrates reproducible reduction behavior for two model reactions and observed rate constants that compare favorably with other copper nanoparticle catalysts, particularly in terms of rate constants normalized for available surface area and including catalysts produced via traditional synthetic methods.

Synthesis and optimization of Pt nanoparticle catalyst supported on heterogeneous composite Mo2C-N-C for acidic direct methanol fuel cell anodes

Molybdenum carbide (Mo2C) has similar d-band characteristics to platinum (Pt), so it has a similar catalytic activity to Pt. It can be used as a catalyst support or co-catalyst in the anode of direct methanol fuel cells (DMFC). The unique hexagonal crystal system structure of Mo2C is beneficial for improving the overall performance of the catalyst when combined with N-doped carbon (N-C). When Pt is loaded onto the Mo2C-N-C support, the synergistic effect between Mo2C-N-C and Pt makes the catalyst exhibit higher activity and stability in the methanol oxidation reaction. In this study, a high-quality Mo2C-N-C support was synthesized using stripped g-C3N4 as a self-sacrificing template, followed by the preparation of Pt/Mo2C-N-C catalyst via microwave-assisted glycol reduction. In acid media, the optimized Pt/Mo2C-N-C catalyst exhibited improved methanol oxidation reaction (MOR) activity and robust durability, the methanol oxidation current density reached 1.74 times that of commercial Pt/C, which was prepared under the same conditions, demonstrating the catalyst’s superior methanol oxidation activity.

Removal of bisphenol A through peroxymonosulfate activation with N-doped graphite carbon spheres coated cobalt nanoparticles catalyst: Synergy of nonradicals

Removal of bisphenol A through peroxymonosulfate activation with N-doped graphite carbon spheres coated cobalt nanoparticles catalyst: Synergy of nonradicals

Performance constraints of high temperature polymer electrolyte membrane fuel cells by varying the Pt/C ratio of the catalyst

Electrodes prepared from catalysts with Pt weight percentages on the carbon support (Pt/C nanoparticles) ranging from 10 up to 60 wt% are used as cathodes of membrane electrode assemblies (MEAs) and tested in high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). For each Pt/C percentage in the catalyst, the cathode Pt-loading (which become proportional to the thickness of the electrode formed by the catalyst nanoparticles) is stepwise scanned from low to high loadings. Results show that when the Pt load increases, the MEA performance (measured by its power density at 0.6 V) rises initially (due to the increase in the number of active sites in the cathode) up to a maximum value limited by the mass transport of oxygen, associated to an optimum Pt-loading (different for each Pt/C ratio). Noteworthy, the peak performance is significantly different depending on the catalyst used (60 > 40 >> 20 > 10 wt% Pt/C), a fact that restricts the catalyst choice according to the performance required by the application. Furthermore, higher amounts of Pt in the cathode lead to a large catalyst waste as the FC performance even decreases as the cathode thickness increases.

Experimental assessment of catalytic biofuel effect on performance and exhaust emission of diesel engine

The present experiment is to analyze the effect of blended biodiesel of chicken fat CF10 (10% chicken fat and 90% diesel), waste cooking oil WC10 (10% waste cooking oil and 90% diesel), and combined chicken fat with waste cooking oil CF&WC10 (5% chicken fat + 5% waste cooking oil and 90% diesel) on the performance of diesel engine. The experiment is conducted at a constant compression ratio of 17, mixing 50 ppm alumina alfa (Al2O3-α) catalyst nanoparticles in each blend. The performance of biodiesel is analyzed at 25%, 50%, 75%, and 100% load conditions and is compared with pure diesel. The results show that the brake torque (BT) and brake power of CF&WC10 were found to be 22.48 Nm and 3.58 kW at full load conditions. However, the indicated thermal efficiency and BTE of CF&WC10 are at full loading conditions of 52.45% and 26.78% respectively. Because the supply of A/F ratio is 18.81, at full load condition and also lowering the brake specific fuel consumption up to 0.32 kg/kWh. Therefore, optimization of both performance and exhaust emission of an engine depends on BTE and NOx as well as HC emissions. Hence, from the emissions reduction point of view, CF&WC10 has lower emissions while achieving brake thermal efficiency similar to diesel fuel. The novelty of research shows CF&WC10 leads to enhanced performance of diesel engine compared to pure diesel fuel.

Pt Nanoparticles on Multi-Walled Carbon Nanotubes with High CO Tolerance for Methanol Electrooxidation.

Anode catalysts are important for direct methanol fuel cells (DMFCs) of energy conversion. Herein, we report a novel strategy by ethylene glycol-based deep eutectic solvents (EG-DESs) for the fabrication of a multi-walled carbon nanotubes (MWCNTs)-supported Pt nanoparticles catalyst (referred to as Pt/CNTs-EG-DES). The Pt/CNTs-EG-DES catalyst provides an increased electrochemically active surface area (ECSA) and shows remarkably improved electrocatalytic performance towards methanol oxidation reaction compared to Pt/CNTs-W (fabricated in water) and commercial Pt/C catalysts. The improved performance is attributed to the generation of more Pt-O bonds which change the electronic states of the Pt atoms and the special node structure that obtains more active sites for a high CO resistance. This study suggests an effective synthesis strategy for Pt-based electrocatalysts with high performance for DMFC applications.

Engineering Chemical and Catalytic Activity of Metal Surface Sites by Controlling Strain and Ligand Effects in Nonmodel Nanoparticle Catalysts

Engineering Chemical and Catalytic Activity of Metal Surface Sites by Controlling Strain and Ligand Effects in Nonmodel Nanoparticle Catalysts

“Sunlight-driven catalytic degradation of MB dye and multi-cycle Re-usability analysis of Cu2-xSe nanoparticles”

One of the best ways to remove organic dyes based contaminant from water resources and industrial waste water is the sunlight driven photo-catalytic degradation method. The theme of the present investigation is the photocatalytic degradation of methylene blue (MB) dye using economically produced Cu2-XSe nanoparticles (NPs) catalyst under solar radiations. The Cu2-XSe NPs crystallized in the cubic structural phase with an average crystallite size around 19 nm. The direct band gap was found to be 2.1 eV. The PL spectra and corresponding CIE diagram show the Cu2-xSe NPs emitted yellow color. The SEM micrographs show that the small grains staked over others to form large grains or patches. The FTIR and EDX spectra confirmed the formation of Cu2-XSe NPs. The obtained optimum photocatalytic degradation efficiency for Cu2-XSe NPs is 90.3 %. For first cycle analysis. The pseudo-first order and second order models were used to analyze the kinetic data of Cu2-XSe NPs for varying concentrations. The multiple-cycle degradation analysis by catalyst of MB dye in one day spam for continuous four cycles were also analysed and discussed. The sun light driven multi-cycle catalytic degradation confirms the re-usability of Cu2-xSe NPs for the treatment of industrial waste water and other contaminated water bodies for the survival of aquatic life and for saving environment.

Electronic effect in bromide-modified noble metal catalysts promotes highly stable and selective hydrogenation

Halides with strong affiliation to metals are traditionally viewed as positions in heterogeneous catalysis. This study introduces a method to enhance the selective hydrogenation performance of noble metal nanoparticle catalysts (Pd, Pt, and Rh hosted on N-doped carbon, SiO2, and Al2O3) by gas-phase bromination with 1-bromooctane. Brominated Pd catalysts, particularly those supported on N-doped carbon, show significant improvements in total butene selectivity and stability in butadiene hydrogenation reactions, displaying >97.5 % selectivity to total butenes at complete conversion with 50 h stable performance even at excessive H2 (H2:butadiene = 50) and a high temperature of 473 K. Comprehensive characterizations coupled with density functional theory calculations reveal that bromide species enhance selective hydrogenation by preferentially adsorbing at stepped Pd sites, altering reaction kinetics and preventing over-hydrogenation. Bromination influences reactant and intermediate adsorption, leading to increased competitive adsorption compared to pristine catalysts. Chemisorption studies on butadiene and 1-butene support altered kinetic behaviors post-bromination. X-ray photoelectron spectroscopy analysis demonstrate an increase in surface Pdδ+ species, owing to the electron-pulling character of nearby adsorbed bromide. In situ diffuse reflection infrared Fourier transform spectroscopy with CO probe molecules confirms Br species adsorption at unsaturated Pd sites. Overall, the study provides an effective approach to tuning the electronic properties of metal catalysts and highlights the positive impact of bromination on improving the hydrogenation performance.

Highly stable and active catalyst in fuel cells through surface atomic ordering.

Shape-controlled alloy nanoparticle catalysts have been shown to exhibit improved performance in the oxygen reduction reaction (ORR) in liquid half-cells. However, translating the success to catalyst layers in fuel cells faces challenges due to the more demanding operation conditions in membrane electrode assembly (MEA). Balancing durability and activity is crucial. Here, we developed a strategy that limits the atomic diffusion within surface layers, fostering the phase transition and shape retention during thermal treatment. This enables selective transformation of platinum-iron nanowire surfaces into intermetallic structures via atomic ordering at a low temperature. The catalysts exhibit enhanced MEA stability with 50% less Fe loss while maintaining high catalytic activity comparable to that in half-cells. Density functional calculations suggest that the ordered intermetallic surface stabilizes morphology against rapid corrosion and improves the ORR activity. The surface engineering through atomic ordering presents potential for practical application in fuel cells with shape-controlled Pt-based alloy catalysts.

Fuel Cell Catalyst Layers with Platinum Nanoparticles Synthesized by Sputtering onto Liquid Substrates.

Platinum (Pt) nanoparticles are widely used as catalysts in proton exchange membrane fuel cells. In recent decades, sputter deposition onto liquid substrates has emerged as a potential alternative for nanoparticle synthesis, offering a synthesis process free of contaminant oxygen, capping agents, and chemical precursors. Here, we present a method for the synthesis of supported nanoparticles based on magnetron sputtering onto liquid poly(ethylene glycol) (PEG) combined with a heat-treatment step for attachment of nanoparticles to a carbon support. Transmission electron microscopy imaging reveals Pt nanoparticle growth during the heat-treatment process, facilitated by the carbon support and the reducing properties of PEG. Following the heat treatment, a bimodal size distribution of Pt nanoparticles is observed, with sizes of 2.5 ± 0.8 and 6.7 ± 1.8 nm, compared to 1.8 ± 0.4 nm after sputtering. Synthesized Pt nanoparticles display excellent specific and mass activities for the oxygen reduction reaction, with 1.75 mA/cm2 Pt and 0.27 A/mgPt respectively, measured at 0.9 V vs the reversible hydrogen electrode. The specific activities reported herein outperform literature values of commercial Pt/C catalysts with similar loading and are on par with values of bulk Pt and mass-selected nanoparticles of comparable size. Also, the mass activities agree well with the literature values. The results provide new insights into the growth processes of SoL-synthesized carbon-supported Pt catalyst nanoparticles, and most crucially, the high performance of the synthesized catalyst layers, along with the possibility of nanoparticle growth through a straightforward heat-treatment step at relatively low temperatures, offer a scalable new approach for producing fuel cell catalysts with more efficient material utilization and new material combinations.

Regulating the location relationship between Cu nanoparticles and Pt atoms to enhance the catalytic hydroisomerization performance: Together or apart?

Single atom catalysts have been recently reported as the efficient catalysts for hydroisomerization compared to the conventional nanoparticle catalyst. Despite the fascinating advantage in enhancing the metal activity or reducing the catalyst cost, the long-term stability of the single atom catalyst seemed not that satisfactory, especially when reacting under atmospheric pressure. Herein, Pt single atom catalysts were combined with Cu nanoparticles by different means to explore a new way to improve the catalytic performance. Cu nanoparticles were located away from Pt sites to form a binary catalyst, or acted as the support of Pt atoms to form a single atom alloy (SAA) catalyst. With the binary catalyst Pt1–0.1Cu@CS, the conversion of the n-heptane after time on stream of 50 h increased to 70.3 %, higher than Pt1@CS (47.3 %). Besides, excessive Cu nanoparticles in the binary catalyst were found rather harmful to the catalysis instead. However, the SAA catalyst Pt1Cu@SAPO-11 showed a poor activity in hydroisomerization compared to Pt1@CS, indicating that the alloy structure should go against the activation of reactant. The roles of Pt atoms and Cu nanoparticles in different catalysts were discussed in detail. The reaction mechanism of hydroisomerization was refined with the different functions of the dual metal sites. This work might be instructive for the design of single atom catalysts combined with metal nanoparticles.