Nanoparticle Catalysts Research Articles

General synthesis of secondary imines via reductive coupling of carbonyl and nitro compounds employing a reusable cobalt catalyst

Reusable nitrogen-doped carbon-encapsulated Co nanoparticle catalysts are found robust for the synthesis of secondary imines via the reductive amination of carbonyl compounds with NH3 or directly with nitro compounds.

Purified CaO supported Pt nanoparticles for the selective hydrogenation of styrene oxide with enhanced selectivity of 1-phenylethanol

The purified CaO supported Pt nanoparticles exhibit the best selectivity toward 1-phenylethanol in the selective hydrogenation of styrene oxide.

Selective catalytic hydrogenation of 5-hydroxymethylfurfural over silica supported FeCoNiCuRu high-entropy alloy nanoparticles

A simple organic ligand chelate-assisted thermal-reduction method provides a universal strategy for generating high-entropy alloy (HEA) nanoparticles catalysts with uniformly dispersed particles for efficient catalytic hydrogenation.

Controlling Pt nanoparticle sintering by sub-monolayer MgO ALD thin films.

Metal nanoparticle (NP) sintering is a major cause of catalyst deactivation, as NP growth reduces the surface area available for reaction. A promising route to halt sintering is to deposit a protective overcoat on the catalyst surface, followed by annealing to generate overlayer porosity for gas transport to the NPs. Yet, such a combined deposition-annealing approach lacks structural control over the cracked protection layer and the number of NP surface atoms available for reaction. Herein, we exploit the tailoring capabilities of atomic layer deposition (ALD) to deposit MgO overcoats on archetypal Pt NP catalysts with thicknesses ranging from sub-monolayers to nm-range thin films. Two different ALD processes are studied for the growth of MgO overcoats on Pt NPs anchored on a SiO2 support, using Mg(EtCp)2 and H2O, and Mg(TMHD)2 and O3, respectively. Spectroscopic ellipsometry and X-ray photoelectron spectroscopy measurements reveal significant growth on both SiO2 and Pt for the former process, while the latter exhibits a drastically lower growth per cycle with an initial chemical selectivity towards Pt. These differences in MgO growth characteristics have implications for the availability of uncoated Pt surface atoms at different stages of the ALD process, as probed by low energy ion scattering, and for the sintering behavior during O2 annealing, as monitored in situ with grazing incidence small angle X-ray scattering (in situ GISAXS). The Mg(TMHD)2-O3 ALD process enables exquisite coverage control allowing a balance between physically blocking the Pt surface to prevent sintering and keeping Pt surface atoms free for reaction. This approach avoids the need for post-annealing, hence also safeguarding the structural integrity of the as-deposited overcoat.

Four-step continuous-flow total synthesis of (-)-debromoflustramine B using a chiral heterogeneous Pd NP catalyst.

Various prenylated indoline alkaloids with diverse biological activities, including (-)-debromoflustramine B with significant butyrylcholinesterase inhibitory activity, could be synthesized by dearomative prenylation reactions of tryptophan derivatives. However, previously reported dearomative prenylations were limited to batch reactions at the milligram scale, requiring multistep reactions and complex post-processing to obtain the desired natural products. The more efficient synthesis of alkaloids remains challenging, as does the recovery of expensive catalysts. Herein, we developed a chiral heterogeneous Pd nanoparticle (NP) catalyst supported on a polymer, which produces indoline alkaloids in high yields with excellent enantioselectivities. Additionally, the first gram-scale four-step continuous-flow total synthesis of (-)-debromoflustramine B was successfully achieved with this chiral Pd heterogeneous catalyst, requiring only a simple post-processing step.

Effective treatment of 2,4,6-trinitrotoluene from aqueous media using a sono-photo-Fenton-like process with a zero-valent iron nanoparticle (nZVI) catalyst.

In this study, we examine the effectiveness of using a combination of a sono-photo-Fenton-like procedure and nano zero-valent iron catalyst (nZVI) to treat 2,4,6-trinitrotoluene (TNT) in an aquatic environment. Zero-valent iron particles were generated by a chemical reduction technique. nZVI nanoparticles were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD) to characterize the nanocatalyst. The resulting nZVI nanoparticles were used as an addition in a sono-photo-Fenton method to remediate an aqueous solution contaminated with TNT. Furthermore, influences of operational factors such as temperature, catalyst dosage, wavelength, ultraviolet power, ultrasonic frequency and power, pH level, H2O2/nZVI ratio, initial TNT concentration, and reaction duration on the treatment of TNT were investigated. Under the conditions of an ideal pH of 3, temperature range of 40-45 °C, concentration of 50 mg per L TNT, dose of 2 mM of nZVI, and ratio of H2O2/Fe0 of 20, a treatment efficiency of 95.2% was achieved after a duration of 30 minutes. The sono-photo-Fenton process combined with nZVI showed a higher TNT removal efficiency compared to the Fenton, sono-Fenton, and photo-Fenton processes under the same conditions. Moreover, it promises a potential solution to treat TNT at the pilot scale while allowing reuse of the nZVI catalyst and the limitation of sludge.

Structure control and evolution of atomically precise gold clusters as heterogeneous precatalysts.

Metal clusters have distinct features from single atom and nanoparticle (>1 nm) catalysts, making them effective catalysts for various heterogeneous reactions. Nevertheless, the ambiguity and complexity of the catalyst structure preclude in-depth mechanistic studies. The evolution of metal species during synthesis and reaction processes represents another challenge. One effective solution is to precisely control the structure of the metal cluster, thus offering a well-defined pre-catalyst. The well-defined chemical formula and configurations make atomically precise metal nanoclusters optimal choices. To fabricate an atomically precise metal nanocluster-based heterogeneous catalyst with enhanced performance, careful structural design of both the nanocluster and support material, an effective assembling technique, and a pre-treatment method for these hybrids need to be developed. In this review, we summarize recent advances in in the development of heterogeneous catalysts using atomically precise gold and alloy gold nanoclusters as precursors. We will begin with a brief introduction to the structural properties of atomically precise nanoclusters and structure determination of cluster/support hybrids. We will then introduce heterogeneous catalysts prepared from medium size (tens to hundreds of metal atoms) and low nuclearity nanoclusters. We will illustrate how ligand modification, support-cluster interaction, hybrid fabrication, and heteroatom (Pt, Pd Ag, Cu, Cd, Fe) introduction affect the structural properties and pretreatment/reaction-induced structural evolution of gold nanocluster pre-catalysts. Lastly, we will highlight the synthetic method of NCs@MOF hybrids and their effectiveness in circumventing the adverse cluster structural evolution. These findings are expected to shed light on the structure-activity relationship studies and future catalyst design strategies using atomically precise metal nanocluster pre-catalysts.

Hierarchical zeolite-encapsulated metal nanoparticles for heterogeneous catalysis.

Zeolites, characterized by their highly porous structure, have become integral to modern industry and environmental science due to their broad applications in adsorption, separation, and catalysis. Recent advancements in zeolite synthesis, particularly through hydrothermal methods and the incorporation of metal nanoparticles, have significantly expanded their utility. This review delves into the innovative strategies for encapsulating metal nanoparticles within zeolite matrices, enhancing catalytic reactions' efficiency, selectivity, and durability. Challenges such as nanoparticle agglomeration and catalyst deactivation are addressed through hierarchical zeolite encapsulation, which provides a novel route for the development of multifunctional materials. By examining methods ranging from in situ encapsulation to post-synthetic recrystallization, this review highlights the versatility and potential of metal@zeolite catalysts in various applications, including organic synthesis, pollutant treatment, and energy conversion. The review underscores the importance of optimizing the interaction between metal nanoparticles and the zeolite framework to achieve superior catalytic performance, offering new directions for research in catalytic science and industrial process optimization.

Integrating single atoms with nanoparticle catalysts for efficient electrochemical energy conversion

This review summarizes the development (integrated effects, classifications, and applications) of emerging catalysts that integrate single atoms with nanoparticles (SA/NPCs). It also highlights the future challenges and opportunities in this field.

Promoting CO2 electroreduction to CO by a graphdiyne-stabilized Au nanoparticle catalyst.

The electrochemical CO2 reduction reaction (CO2RR) gives an ideal approach for producing valuable chemicals, offering dual benefits in terms of environmental preservation and carbon recycling. In this work, a strong synergistic effect is constructed by adopting electron-rich graphdiyne (GDY) as the supporting matrix, which significantly stabilizes the Au active sites and boosts the CO2RR process. The as-prepared GDY-supported Au nanoparticles (Au/GDY) exhibit excellent CO2RR performance, with an extremely high faradaic efficiency of 94.6% for CO as well as good stability with continuous electrolysis for 36 hours. The superior activity and stability of the Au/GDY catalyst can be attributed to the electronic interaction between Au nanoparticles and the GDY substrate, resulting in enhanced electron transfer rates and a stable network of catalytically active sites that ultimately promote the CO2RR.

Synthesis of an MXene supported Co nanoparticle catalyst for efficient catalytic transfer hydrogenation of nitro compounds with formic acid

The developed 2.6% Co/MXene exhibited excellent catalytic performance for the catalytic transfer hydrogenation of readily available nitroarenes employing HCOOH, leading to the specific generation of essential and versatile formamides.

Atomically dispersed cobalt catalysts for tandem synthesis of primary benzylamines from oxidized β-O-4 segments.

This work presents an innovative approach focusing on fine-tuning the coordination environment of atomically dispersed cobalt catalysts for tandem synthesis of primary benzylamines from oxidized lignin model compounds. By meticulously regulating the Co-N coordination environment, the activity of these catalysts in the hydrogenolysis and reductive amination reactions was effectively controlled. Notably, our study demonstrates that, in contrast to cobalt nanoparticle catalysts, atomically dispersed cobalt catalysts exhibit precise control of the sequence of hydrogenolysis and reductive amination reactions. Particularly, the CoN3 catalyst with a triple Co-N coordination number achieved a remarkable 94% yield in the synthesis of primary benzylamine. To our knowledge, there is no previous documentation of the synthesis of primary benzylamines from lignin dimer model compounds. Our study highlights a promising one-pot route for sustainable production of nitrogen-containing aromatic chemicals from lignin.

Bifunctional Pt–Ir nanoparticle catalysts for oxygen reduction and evolution reactions: investigating the influence of surface composition on the catalytic properties

Unitized regenerative fuel cells demand efficient bifunctional catalysts for oxygen reduction and evolution reactions. Here, we study iridium-decorated platinum nanoparticles. Ir40/Pt60 displayed the highest OER mass activity, surpassing Ir black, whereas Ir20/Pt80 showed the highest efficiency.

Heterogeneously catalyzed decarbonylation of thioesters by supported Ni, Pd, or Rh nanoparticle catalysts.

Decarbonylation of thioesters has been actively studied using homogeneous metal catalysts as an attractive approach for synthesizing thioethers, which are widely utilized in various fields, because decarbonylation ideally requires no additives and produces CO as the sole theoretical byproduct. However, heterogeneously catalyzed decarbonylation of thioesters has not been reported to date, despite its importance for the construction of environmentally-friendly and practical catalytic systems. This study demonstrated a heterogeneously catalyzed system for the decarbonylation of various aryl thioesters to produce thioethers and CO by utilizing CeO2- or hydroxyapatite-supported Ni, Pd, or Rh nanoparticle catalysts. The Ni catalysts showed high catalytic activity, while the Pd catalysts possessed excellent functional group tolerance. The Rh catalysts were suitable for the selective decarbonylation of unsymmetrically substituted thioesters.

Dehydrogenative oxidation of hydrosilanes using gold nanoparticle deposited on citric acid-modified fibrillated cellulose: unveiling the role of molecular oxygen.

Efficient and environmentally friendly synthesis of silanols is a crucial issue across the broad fields of academic and industrial chemistry. Herein, we describe the dehydrogenative oxidation of hydrosilane using a gold nanoparticle catalyst supported by fibrillated citric acid-modified cellulose (F-CAC). Au:F-CAC catalysts with various particle sizes (1.7 nm, 4.9 nm, and 7.7 nm) were prepared using the trans-deposition method, a technique previously reported by our group. These catalysts exhibited significant catalytic activity to produce silanols with high turnover frequency (TOF) of up to 7028 h-1. Recycling experiments and transmission electron microscopy (TEM) observation represented the high durability of Au:F-CAC under the reaction conditions, allowing kinetic studies on size dependency. Mechanistic studies were conducted, including isotope labelling experiments, kinetics, and various spectroscopies. Notably, the near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) of the model catalyst (Au:PVP) revealed the formation of catalytically active cationic Au sites on the surface through the adsorption of molecular oxygen, providing a new insight into the reaction mechanism.

A Well-Defined Supported Pt Nanoparticle Catalyst for Heterogeneous Catalytic Surface Science

Our ability to rationalise the activity of heterogeneous catalytic materials relies on a precise understanding of both the structure and composition of the catalyst under reaction conditions to resolve active...

Promoted oxygen reduction performance enabled by Co/Cu nanoparticles encapsulated in carbon nanotubes for long-life flexible and rechargeable Zn–air batteries

A simple and inexpensive method to prepare efficient bifunctional nitrogen-doped carbon nanotube-encapsulated copper and cobalt nanoparticle catalysts.

Heterogeneously catalyzed thioether metathesis by a supported Au-Pd alloy nanoparticle design based on Pd ensemble control.

C-S bond metathesis of thioethers has gained attention as a new approach to the late-stage diversification of already existing useful thioethers with molecular frameworks intact. However, direct or indirect thioether metathesis is scarcely reported, and heterogeneously catalyzed systems have not been explored. Here, we develop heterogeneously catalyzed direct thioether metathesis using a supported Au-Pd alloy nanoparticle catalyst with a high Au/Pd ratio. The Au-diluted Pd ensembles suppress the strong π-adsorption of diaryl thioethers on the nanoparticles and promote transmetalation via thiolate spill-over onto neighboring Au species, enabling an efficient direct thioether metathesis.

Atomic doping to enhance the p-type behavior of BiFeO3 photoelectrodes for solar H2O2 production

Na-doped BiFeO3 demonstrates an enhanced p-type behavior compared to p-type BiFeO3 prepared without extrinsic dopants, and Na-doped BiFeO3 can serve as a photocathode for solar O2 reduction to H2O2 when coupled with Ag nanoparticle catalysts.

Enhancing the performance of heterogeneous palladium based catalysts in the mild reductive depolymerization of soda lignin through addition of a non-noble metal and tuning of the preparation strategy

Addition of a non-noble metal and tuning of the preparation strategy, can dramatically reduce the synthesis costs of Pd nanoparticle catalysts while also increasing activity and steering product selectivity.