Dendrimer-encapsulated Nanoparticles Research Articles

Hexabranched dendrimers encapsulated metallic copper nanoparticles and their catalytic evaluation for the conversion of para-nitrophenol to para-aminophenol

Two new hexanuclear copper (II) complexes, [Cu6(G2hexpyD)(DMF)24](TFA)12 and [Cu6(G2hexbzaD)(DMF)18](TFA)12, where G2hexpyD and G2hexbzaD are second-generation dendrimers (G = 2) and TFA is trifluoroacetate, have been synthesized. The prepared copper (II) complexes have been fully characterized. Furthermore, to prepare dendrimer encapsulated copper nanoparticles (G2dendrimer-CuNPs), metal ions were chemically reduced by NaBH4 in 2-methoxyethanol, which yielded zero-valent metal particles with a narrow size distribution. The catalytic reduction of para-nitrophenol to para-aminophenol by G2dendrimer-CuNPs was evaluated in the presence of NaBH4. The reduction reaction was completed in 3 min. The reaction progress was monitored by electronic absorption spectroscopy. The rate constant was calculated to be 0.0073 and 0.0079 s−1 for G2hexbzaD-CuNPs and G2hexpyD-CuNPs, respectively. The results revealed that G2dendrimer-CuNPs exhibit high catalytic performance in the conversion of para-nitrophenol to para-aminophenol. Easy separation, low price, high recyclability and great efficiency are the main advantages of G2dendrimer-CuNPs that make them as the suitable catalysts for the catalytic reduction of para-nitrophenol.

Single atoms and small clusters of atoms may accompany Au and Pd dendrimer-encapsulated nanoparticles

We report the presence of small clusters of atoms (<1 nm) (SCs) and single atoms (SAs) in solutions containing 1-2 nm dendrimer-encapsulated nanoparticles (DENs). Au and Pd DENs were imaged using aberration-corrected scanning transmission electron microscopy (ac-STEM), and energy dispersive spectroscopy (EDS) was used to identify and quantify the SAs/SCs. Two main findings have emerged from this work. First, the presence or absence of SAs/SCs depends on both the terminal functional group of the dendrimer (-NH2 or -OH) and the elemental composition of the DENs (Au or Pd). Second, dialysis can be used to remove the majority of SAs/SCs in cases where a high density of SAs/SCs are present. The foregoing conclusions provide insights into the mechanisms for Au and Pd DEN synthesis and stability. Ultimately, these results demonstrate the need for careful characterization of systems containing nanoparticles to ensure that SAs/SCs, which may be below the detection limit of most analytical methods, are taken into consideration (especially for catalysis experiments).

Turn-On Fluorescence Sensing of Oxygen with Dendrimer-Encapsulated Platinum Nanoparticles as Tunable Oxidase Mimics for Spatially Resolved Measurement of Oxygen Gradient in a Human Gut-on-a-Chip.

Turn-on type fluorescence sensing of O2 is considered a promising approach to developing ways to measure O2 in microenvironments with spatially distributed O2 levels. As a class of nanomaterials with a high degree of control over composition and structure, dendrimer-encapsulated nanoparticles (DENs) are promising candidates to mimic biological enzymes. Here, we report a strategy to monitor spatially distributed O2 across a three-dimensional (3D) human intestinal epithelial layer in a gut-on-a-chip in a turn-on fluorescence sensing manner. The strategy is based on the oxidase-mimetic activity of Pt DENs for catalytic oxidation of nonfluorescent Amplex Red to highly fluorescent resorufin in the presence of O2. We synthesized Pt DENs using two different types of dendrimers (i.e., amine-terminated or hydroxyl-terminated generation 6 polyamidoamine (PAMAM) dendrimers) with six different Pt2+/dendrimer ratios (i.e., 55, 200, 220, 550, 880, and 1320). After clarifying the intrinsic oxidase-mimetic activity of Pt DENs, we determined tunable oxidase-mimetic activity of Pt DENs, especially with fine-tuning the ratios of the Pt precursor ions and dendrimers. Particularly, the optimal Pt DENs having a Pt2+/dendrimer ratio of 1320 exhibited an ∼117-fold increase in the oxidase-mimetic activity for catalyzing the aerobic oxidation of Amplex Red to resorufin compared to one having a Pt2+/dendrimer ratio of 200. This study exemplified a simple yet effective approach for spatially resolved imaging of O2 using metal nanoparticle-based oxidase mimics in microphysiological environments like a human gut-on-a-chip.

A review on poly(amidoamine) dendrimer encapsulated nanoparticles synthesis and usage in energy conversion and storage applications

A review on poly(amidoamine) dendrimer encapsulated nanoparticles synthesis and usage in energy conversion and storage applications. • The Dend-NPs for electrochemical energy conversion and storage is reviewed. • Synthesis methods to prepare active and durable Dend-NPs are summarized. • The best practice and beforehand knowledge of Dend-NPs are recommended. • The electrocatalytic activity of Dend-NPs towards multiple reactions are discussed. • The reasons for high performance in multiple energy systems are highlighted. The direction of this review is concentrating on the development of poly(amidoamine) (PAMAM) dendrimer encapsulated metal nanoparticles (NPs), so-called Dend-NPs as catalysts in the field of electrochemical energy conversion and storage. To date, Dend-NPs have been pointed out as well-organized and effective catalysts in the most popular electrochemical technologies, such as fuel cells, batteries, supercapacitors and water electrolyzers. Different strategies and technological progresses targeting efficient power and energy productions with excellent durability and performance retentions in such systems are emphasized. Dend-NPs action in electrochemical energy systems thrived by cathodic catalytic reactions, particularly, hydrogen evolution reaction (HER) in electrolyzers and oxygen reduction reaction (ORR) in fuel cells, and electrochemical (Faradaic and non-Faradaic) processes in batteries and supercapacitors are summarized. The metal NPs produced within the dendrimer by various approaches, conditions for obtaining zero-valent metals and synthesis methods for different types of metal NPs are discussed. Advancing knowledge of Dend-NPs synthesis, difficulties and their solutions and the best practice recommended for readers are explained in brief. Besides, stability, role of dendrimer, generation effects, terminal group effects and mechanisms to encapsulate each transition and precious metal NPs such as copper (Cu), nickel (Ni), platinum (Pt), palladium (Pd), silver (Ag), gold (Au) and bimetallic within the cavity of PAMAM dendrimers are highlighted. Moreover, PAMAM dendrimer and its generation are classified bearing in mind their viable use in energy technologies and applications where possible.

PAMAM (poly-amido amine) dendrimer supported copper nanoparticles for chemoselective nitro reduction

Present paper reports the synthesis of biocompatible poly (amidoamine) (PAMAM) dendrimer by Michael addition (up to Generation 2) which has been used as a matrix for preparing copper nanoparticles using green solvent. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy – dispersive X-ray spectroscopy (EDX) were used to determine the surface morphology and elemental composition of the nanoparticle. The results confirmed the FCC structure of the prepared dendrimer encapsulated Cu nanoparticles with an average crystallite size of 4 ​nm. Purely aqueous-phase chemoselective reduction of nitro group in various aromatic nitro substrates such as p-nitrophenol, p-nitrobenzaldehyde and 2, 4 dinitrophenol have been employed in the presence of eco-friendly dendrimer encapsulated Cu nanoparticles using hydrazine hydrate as reducing agent. The nanocatalyst showed high reusability up to seven runs exhibiting no significant loss in its catalytic activity. As the synthesised material is found to be biocompatible, this catalytic strategy can be used to catalyse similar biochemical reactions.

Electrochemical Cleaning Stability and Oxygen Reduction Reaction Activity of 1‐2 nm Dendrimer‐Encapsulated Au Nanoparticles

AbstractHere we show that just three electrochemical scans to modest positive potentials result in substantial growth of 1–2 nm Au dendrimer‐encapsulated nanoparticles (DENs). We examined two sizes of Au DENs, denoted as G6‐NH2(Au147) and G6‐NH2(Au55), where G6‐NH2 represents a sixth‐generation, amine‐terminated, poly(amidoamine) dendrimer and the subscripts, 147 and 55, represent the average number of atoms in each size of DENs. Ex situ transmission electron microscopy (TEM) and in situ X‐ray absorption spectroscopy (XAS) results indicate that G6‐NH2(Au55) DENs grow to the same size as the G6‐NH2(Au147) DENs following these scans. Importantly, this growth occurs prior to the onset of detectable faradaic Au oxidation or reduction current. The observed growth in the size of the DENs directly correlates to changes in the electrocatalytic ORR activity. The key point is that after just three positive scans the G6‐NH2(Au147) and G6‐NH2(Au55) DENs are essentially indistinguishable in terms of both physical and electrocatalytic properties.

Metal-Organic Frameworks-Based Nanomaterials for Drug Delivery.

The composition and topology of metal-organic frameworks (MOFs) are exceptionally tailorable; moreover, they are extremely porous and represent an excellent Brunauer–Emmett–Teller (BET) surface area (≈3000–6000 m2·g−1). Nanoscale MOFs (NMOFs), as cargo nanocarriers, have increasingly attracted the attention of scientists and biotechnologists during the past decade, in parallel with the evolution in the use of porous nanomaterials in biomedicine. Compared to other nanoparticle-based delivery systems, such as porous nanosilica, nanomicelles, and dendrimer-encapsulated nanoparticles, NMOFs are more flexible, have a higher biodegradability potential, and can be more easily functionalized to meet the required level of host–guest interactions, while preserving a larger and fully adjustable pore window in most cases. Due to these unique properties, NMOFs have the potential to carry anticancer cargos. In contrast to almost all porous materials, MOFs can be synthesized in diverse morphologies, including spherical, ellipsoidal, cubic, hexagonal, and octahedral, which facilitates the acceptance of various drugs and genes.

Multicompartment dendrimicelles with binary, ternary and quaternary core composition.

Hierarchically built-up multicompartment nanoaggregate systems are of interest for, e.g., novel materials and medicine. Here we present a versatile strategy to generate and unambiguously characterize complex coacervate-core micelles by exploiting four different dendrimeric subcomponents as core-units. The resulting mesoscale structures have a hydrodynamic diameter of 50 nm and a core size of 33 nm, and host about thirty 6th generation polyamidoamine (PAMAM) dendrimers. We have used FRET (efficiency of ∼0.2) between fluorescein and rhodamine moieties immobilized on separate PAMAM dendrimers (G6-F and G6-R, respectively) to prove synchronous encapsulation in the micelle core. Tuning the proximity of the FRET pair molecules either by varying the G6-F : G6-R ratio, or by co-assembling non-functionalized dendrimer (G6-E) in the core, reveals the optimal FRET efficiency to occur at a minimum of 70% loading with G6-F and G6-R. Additional co-encapsulation of 6th generation gold dendrimer-encapsulated nanoparticles (G6-Au) in the micelle core shows a dramatic reduction of the FRET efficiency, which can be restored by chemical etching of the gold nanoparticles from within the micellar core with thiols, leaving the micelle itself intact. This study reveals the controlled co-assembly of up to four different types of subcomponents in one single micellar core and concomitantly shows the wide variety of structures that can be made with a well-defined basic set of subcomponents. It is straightforward to design related strategies, to incorporate inside one micellar core, e.g., even more than 4 different dendrimers, or other classes of (macro)molecules, with different functional groups, other FRET pairs or different encapsulated metal nanoparticles.

Synthesis and Applications of Dendrimer-Encapsulated Pt Nanoparticles in Chemical Sensors

Synthesis of nanoparticles having well-defined small sizes especially less than ~3 nm has been in the forefront of research attention in diverse fields including biological and chemical sensors because of unique features of such very small particles. Synthesis and characterization of such tiny particles still remains challenging due to the extremely small dimension of the particles, too. Here, I present the synthesis of ultra-small Pt nanoparticles having different but uniform sizes using dendrimers as a molecular template, which is usually denominated as dendrimer-encapsulated nanoparticles (DENs). Specifically, I present a new synthesis strategy of Pt DENs to expand the applicable number of Pt atoms in Pt DENs by utilizing repetitively coupled chemical reduction and galvanic exchange reactions. The applications of Pt DENs is also discussed in chemical sensors. For example, I present the modification of indium tin oxide (ITO) with Pt DENs to provide enhanced stable electrochemiluminescence (ECL) of Ru(bpy)3 2+/tripropylamine while preserving optical transparency of ITO for sensitive ECL-based analyses.

Composition-dependent catalytic activity of bimetallic PtPd dendrimer-encapsulated nanoparticles having an average size of 1.7 nm for hydrolytic dehydrogenation of ammonia borane

We investigated composition-dependent catalytic activity of bimetallic PtPd dendrimer-encapsulated nanoparticles (DENs) that had a uniform size of ∼1.7nm for hydrolytic dehydrogenation of ammonia borane (AB). The PtPd DENs, composed of seven different Pt: Pd ratios, were synthesized using hydroxyl-terminated sixth-generation polyamidoamine dendrimers as a molecular template. The dendrimer-templating method allowed for synthesizing bimetallic PtPd DENs with controllable nanoparticle composition while fixing the size of the nanoparticles uniformly at ∼1.7 nm. Compared with monometallic Pt and Pd DENs, the bimetallic PtPd DENs showed superior catalytic activity for the hydrolytic dehydrogenation of AB. Furthermore, the bimetallic PtPd DENs exhibited composition-dependent activity with the maximum activity (i.e., average turnover frequency=108.5±15.9molH2·molatom Pt+pd−1·min−1) at a Pt: Pd ratio of 1:1 for the catalytic hydrolysis of AB.

Single-Walled Carbon Nanotubes Decorated with Dendrimer-Encapsulated Platinum Nanoparticles as Catalytic Immobilization Matrix for Amperometric Sensing of Glutamate.

Herein, we report the functional decoration of single-walled carbon nanotubes (swCNTs) with Pt dendrimer-encapsulated nanoparticles (Pt DENs) (dia. (1.78 ± 0.18) nm) for the amperometric sensing of glutamate. The functional decoration of swCNTs was carried out via electrochemical grafting of Pt DENs onto swCNTs, and subsequent cross-linking of glutamate oxidase (GluOx) enzymes to the grafted Pt DENs on swCNT surfaces. The critical role of Pt DENs as catalytic immobilization matrix allowed both the immobilization of GluOx enzymes while maintaining the enzymatic activity of GluOx, and the electrocatalytic oxidation of H₂O₂ generated enzymatically in the presence of glutamate. Taking advantage of Pt DENs as catalytic immobilization matrix, the resulting swCNTs films, denoted as GluOx/Pt DEN/swCNTs, were applied as amperometric sensing platforms that display superior analytical characteristics, including sensitivity, selectivity, stability, and reproducibility, to the non-catalytic counterpart (i.e., GluOx/swCNTs), which led to the promising application of GluOx/Pt DEN/swCNTs to the practical analysis of glutamate in real samples.

New Horizon of Nanoparticle and Cluster Catalysis with Dendrimers.

Among various approaches synthesizing metal nanoparticles and tiny clusters, a template method using dendrimers has significant advantages over other chemical approaches with respect to their synthetic precision and the scalability. A dendrimer of polydentate ligands assembles metal ions or salts into the interior allowing production of metal nanoparticles in the dendrimer. The dendrimer-encapsulated nanoparticles (DENs) exhibit unique and remarkable catalytic properties depending on the size and elemental formula. Recent advances in dendrimer chemistry even enabled the atom precise synthesis of subnanometer metal clusters that have been impossible to prepare by wet chemical methods. In addition, not only for the synthesis of metal nanoparticles and clusters, the dendrimer itself can also provide the modulation of activity and selectivity in the catalysis. In this review, we summarized the most relevant research in which the dendrimer was employed as the template, modulator, or stabilizer for nanoparticle synthesis for catalytic applications.

Carboxylative Cyclization of Propargylic Amines with Carbon Dioxide­ Catalyzed by Poly(amidoamine)-Dendrimer-Encapsulated Gold Nanoparticles

We prepared gold nanoparticles encapsulated in poly(amidoamine) (PAMAM) dendrimers as templating agents. The resulting gold nanoparticles were used as catalysts for the carboxylative cyclization of propargylic amines with carbon dioxide to afford the corresponding 1,3-oxazolidin-2-ones in yields of up to 99%.

Catalytic activity of different sizes of Ptn/Co3O4 in the oxidative degradation of Methylene Blue with H2O2

In this work, we demonstrate the catalytic activity and kinetic analyses of generation six poly(amido-amine) hydroxyl-terminated (PAMAM), G6-OH(Ptn) (n = 55, 140, 225) dendrimer-encapsulated nanoparticles (DENs) immobilized onto mesoporous cobalt oxide (Co3O4) for the catalytic oxidation of methylene blue (MB). Ultra-Violet Visible (UV–Vis) spectrophotometry showed the ligand to metal charge transfer (LMCT) band of metal precursor ions coordinated to the tertiary amines of the dendrimer. The size of fully reduced Pt DENs and supported Pt nanoparticles were investigated using High-Resolution Transmission Electron Microscopy (HR-TEM). The mesoporous Co3O4 was synthesized by inverse micelle method, prior to Ptn DENs being supported on the Co3O4 via wet impregnation procedure. The crystallite structure and size of Co3O4 was investigated by powder X-ray diffraction (p-XRD) spectroscopy. Immobilized Ptn/Co3O4 structural analysis was investigated for the pore size and pore volume using N2 sorption techniques. Thermal gravimetric analyses (TGA) also indicated the dendrimer decomposition on the G6-OH(Ptn)/Co3O4 materials to be 550 °C. Hydrogen temperature programmed reduction (H2-TPR) analyses were conducted and the reducibility of the supported cobalt oxide showed only one temperature peak that was ascribed to the reduction of surface lattice oxygens. The experimental kinetic data was analyzed and fitted to the Langmuir-Hinshelwood model using elementary first-order reaction kinetics and the thermodynamic parameters were calculated. Catalyst Pt55/Co3O4 showed stability during the reusability investigation of up to 8 cycles. The G6-OH(Ptn) were immobilized on silica and tested for catalytic oxidation of MB as a control experiment.

Nanoparticles reveal Extreme Size-Sorting and Morphologies in Complex Coacervate Superstructures

We here provide detailed insight in self-assembled complex coacervate systems exploiting gold nanoparticles for cryoTEM contrast. Nanoparticle-containing dendrimicelles are formed from fifth-generation dendrimer-encapsulated nanoparticles (DENs) and dendrimer-stabilized nanoparticles (DSNs). The complex coacervate structures self-organize in biconcave thin water layers into size-sorted monolayer superstructures. The embedded nanoparticles are a straightforward tool to visualize dendrimicelles and determine the aggregation number and polydispersity. The superstructure shows extreme size-sorting patterns which, contrary to related systems with higher generation dendrimers, consists not only of dendrimicelles but also much bigger complex coacervate nanoassemblies, such as vesicles.

A Facile and Scalable Route to the Preparation of Catalytic Membranes with in Situ Synthesized Supramolecular Dendrimer Particle Hosts for Pt(0) Nanoparticles Using a Low-Generation PAMAM Dendrimer (G1-NH2) as Precursor.

Since the first reports of Cu dendrimer-encapsulated nanoparticles (DENs) published in 1998, the dendrimer-templating method has become the best and most versatile method for preparing ultrafine metallic and bimetallic nanoparticles (1-3 nm) with well-defined compositions, high catalytic activity, and tunable selectivity. However, DENs have remained for the most part model systems with limited prospects for scale up and integration into high-performance and reusable catalytic modules and systems for industrial-scale applications. Here, we describe a facile and scalable route to the preparation of catalytic polyvinylidene fluoride (PVDF) membranes with in situ synthesized supramolecular dendrimer particles (SDPs) that can serve as hosts and containers for Pt(0) nanoparticles (2-3 nm). These new catalytic membranes were prepared using a reactive encapsulation process similar to that utilized to prepare Pt DENs by addition of a reducing agent (sodium borohydride) to aqueous complexes of Pt(II) + G4-OH/G6-OH polyamidoamine (PAMAM) dendrimers. However, the SDPs (2.4 μm average diameter) of our new mixed matrix PVDF-PAMAM membranes were synthesized in the dope dispersion without purification prior to film casting using (i) a low-generation PAMAM dendrimer (G1-NH2) as particle precursor and (ii) epichlorohydrin, an inexpensive functional reagent, as cross-linker. In addition, the membrane PAMAM particles contain secondary amine groups (∼1.9 mequiv per gram of dry membrane), which are more basic and thus have higher Pt binding affinity than the tertiary amine groups of the G4-OH and G6-OH PAMAM dendrimers. Proof-of-concept experiments show that our new PVDF-PAMAM-G1-Pt/membranes can serve as highly active and reusable catalysts for the hydrogenation of alkenes and alkynes to the corresponding alkanes using (i) H2 at room temperature and a pressure of 1 bar and (ii) low catalyst loadings of ∼1.4-1.6 mg of Pt. Using cyclohexene as model substrate, we observed near quantitative conversion to cyclohexane (∼98%). The regeneration studies showed that our new Pt/membrane catalysts are stable and can be reused for five consecutive reaction cycles for a total duration of 120 h including 60 h of heating at 100 °C under vacuum for substrate, product, and solvent removal with no detectable loss of cyclohexene hydrogenation activity. The overall results of our study point to a promising, versatile, and scalable path for the integration of catalytic membranes with in situ synthesized SDP hosts for Pt(0) nanoparticles into high-throughput modules and systems for heterogeneous catalytic hydrogenations, an important class of reactions that are widely utilized in industry to produce pharmaceuticals, agrochemicals, and specialty chemicals.

Electrochemical functionalization of single-walled carbon nanotubes with amine-terminated dendrimers encapsulating Pt nanoparticles: Toward facile field-effect transistor-based sensing platforms

We present a method for functionalization of single-walled carbon nanotubes (CNTs) with amine-terminated dendrimers encapsulating catalytic nanoparticles, and demonstrate the feasibility of functionalized CNTs as efficient field-effect transistor (FET)-sensing platforms. As a model system, we synthesized Pt dendrimer-encapsulated nanoparticles (DENs) using amine-terminated sixth-generation poly(amidoamine) dendrimers, and functionalized CNT-based FET channels with Pt DENs via electro-oxidative grafting of the terminal amines of dendrimers onto the surface of CNTs. We also demonstrated spatially-controlled surface functionalization of CNTs and subsequent modification of the functionalized CNT-based FET channels with glutamate oxidases for efficient FET-based sensing of glutamates. Our approach could facilitate the functionalization of CNTs with a variety of catalytic nanoparticles and biologically active materials, enabling the development of sensitive and selective FET-based sensor devices.

Determination of maximum loading capacity of polyamidoamine (PAMAM) dendrimers and evaluation of Cu55 dendrimer‐encapsulated nanoparticles for catalytic activity

AbstractSpectrophotometric titrations provide information about the interior of the polyamidoamine (PAMAM) dendrimers, and therefore how nanoparticles are encapsulated. In this work, binding studies were performed to determine maximum loading capacities (N) of hydroxyl terminated G4, G5, and G6 PAMAM dendrimers with Cu2+ ions. The values of N found via spectrophotometric titrations were 16.22, 31.86, and 57.36 for G4‐OH, G5‐OH, and G6‐OH, respectively. The determination of loading capacity was also done using Viva spin filtration, and the results were found to be in agreement with those found via spectrophotometric titrations. From the binding isotherm, the values of equilibrium constant (K′) were determined and found to be 0.0488 (G4‐OH), 0.0291 (G5‐OH), and 0.0158 (G6‐OH). Owing to instability of G4‐OH (Cu16), G5‐OH (Cu32), and G6‐OH (Cu57) dendrimer‐encapsulated nanoparticles (DENs) synthesized, G6‐OH (Cu55) DENs of average size 2.6 ± 0.3 nm were prepared and were found to be relatively stable. Thus G6‐OH (Cu55) catalyst was evaluated for the reduction of 4‐nitrophenol and was found to be catalytically active toward reduction of 4‐nitrophenol. Reaction kinetics of 4NP reduction was thoroughly studied in light of the Langmuir‐Hinshelwood kinetic model, and surface rate k, and the adsorption rates K4NP, and KBH4 were determined. The reaction was performed at different temperatures, which further expanded the study into determination of thermodynamic (ΔH‡, ΔS‡, ΔG‡, and EA) parameters.

Structural Characterization of Rh and RhAu Dendrimer-Encapsulated Nanoparticles.

We report the structural characterization of 1-2 nm Rh and RhAu alloy dendrimer-encapsulated nanoparticles (DENs) prepared by chemical reduction with NaBH4. In contrast to previously reported results, in situ and ex situ X-ray absorption spectroscopic experiments indicate that only a fraction of the Rh3+ present in the precursors are reduced by NaBH4. Additional structural analysis of RhAu alloy DENs using extended X-ray absorption fine structure spectroscopy leads to a model in which there is significant segregation of Rh and Au within the nanoparticles. In Rh-rich alloy DENs, Au atoms are segregated on the nanoparticle surface.

Microelectrochemical Flow Cell for Studying Electrocatalytic Reactions on Oxide-Coated Electrodes.

Here, we report a new kind of microelectrochemical flow system that is well suited for studying electrode modifications, like thin films prepared by atomic layer deposition (ALD), that require substrates to have a two-dimensional form factor. The design provides a means for electrodes to be modified ex situ and then incorporated directly into the flow cell. The electrodes can be removed after testing and further modified or tested before being reincorporated into the flow cell. Using this cell, mass-transfer coefficients up to 0.011 cm/s and collection efficiencies up to 57 ± 10% have been achieved. Electrodes modified with an ultrathin layer of ALD Al2O3 and an overlayer of Pt dendrimer-encapsulated nanoparticles (DENs) have been incorporated into the flow cell and their electrocatalytic properties evaluated. Subsequently, the dendrimer was removed from the Pt DENs using a UV/O3 treatment, and this provided direct contact between the Al2O3 layer and the NPs. Finally, the product distribution for the oxygen reduction reaction (water vs H2O2) was evaluated in the presence and absence of Pt-Al2O3 support interactions.