Enhanced electrocatalytic performance of platinum nanoparticles on thiolated polyaniline-multiwalled carbon nanotubes for methanol oxidation

Pt nanoparticles (PtNPs) well-dispersed on thiolated polyaniline (TPANI)-multiwalled carbon nanotubes (MWCNTs) were prepared for enhanced electrocatalytic oxidation of methanol in acidic media. Briefly, the preparation of nanocomposites was carried out via microwave-assisted thiol–ene reaction of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) with oxidized PANI, which was synthesized in the presence of MWCNTs, yielding TPANI-MWCNTs; then, PtNPs were deposited on TPANI-MWCNTs by a microwave-assisted method to obtain PtNPs/TPANI-MWCNT nanohybrids. Fourier transform infrared spectroscopy, cyclic voltammetry (CV), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and inductively coupled plasma-atom emission spectroscopy were used to study relevant nanohybrid properties. TEM showed that PtNPs were well dispersed on TPANI-MWCNTs. TGA showed that PtNPs/TPANI-MWCNTs exhibited better thermal stability than PtNPs/TPANI-MWCNTs and PtNPs/MWCNTs. CV studies showed that PtNPs/TPANI-MWCNT-modified glassy carbon electrode (GCE) exhibited a larger electrochemically active surface area and higher electrocatalytic performance toward methanol electro-oxidation compared with those of PtNPs/PANI-MWCNTs/GCE and PtNPs/MWCNTs/GCE. Also, the PtNPs/TPANI-MWCNTs/GCE electrode possessed high stability and maintained 86% of its initial catalytic activity after 1000-cycle CV in 1.0 M CH₃OH + 0.5 M H₂SO₄.

Pt nanoparticles (PtNPs) well-dispersed on thiolated polyaniline (TPANI)-multiwalled carbon nanotubes (MWCNTs) were prepared for enhanced electrocatalytic oxidation of methanol in acidic media.     

The facile synthesis of core–shell PtCu nanoparticles with superior electrocatalytic activity and stability in the hydrogen evolution reaction

Pt is the most efficient electrocatalyst for the hydrogen evolution reaction (HER); however, it is a high cost material with scarce resources. In order to balance performance and cost in a Pt-based electrocatalyst, we prepared a series of PtCu bimetallic nanoparticles (NPs) with different Pt/Cu ratios through a facile synthetic strategy to optimize the utilization of Pt atoms. PtCu NPs demonstrate a uniform particle size distribution with exposed (111) facets that are highly active for the HER. A synergetic effect between Pt and Cu leads to electron transfer from Pt to Cu, which is favorable for the desorption of H intermediates. Therefore, the as-synthesized carbon black (CB) supported PtCu catalysts showed enhanced catalytic performance in the HER compared with a commercial Pt/C electrocatalyst. Typically, Pt₁Cu₃/CB showed excellent HER performance, with only 10 mV (acid) and 17 mV (alkaline) overpotentials required to achieve a current density of 10 mA cm⁻². This is because the Pt₁Cu₃ NPs, with a small average particle size (7.70 ± 0.04 nm) and Pt–Cu core and Pt-rich shell structure, display the highest electrochemically active surface area (24.7 m² g_Pt⁻¹) out of the as-synthesized PtCu/CB samples. Furthermore, Pt₁Cu₃/CB showed good electrocatalytic stability, with current density drops of only 9.3% and 12.8% in acidic solution after 24 h and in alkaline solution after 9 h, respectively. This study may shed new light on the rational design of active and durable hydrogen evolution catalysts with low amounts of Pt.

A series of PtCu bimetallic nanoparticles with different Pt/Cu ratios was synthesized via a facile synthetic strategy to optimize the utilization of Pt atoms. Pt₁Cu₃/CB showed excellent HER performance under acidic and alkaline conditions.     

Three-dimensional N-doped graphene aerogel-supported Pd nanoparticles as efficient catalysts for solvent-free oxidation of benzyl alcohol

Herein, three-dimensional (3D) nitrogen-doped graphene with large surface areas and abundant porous structures was prepared by a hydrothermal synthesis method, which served as a novel support to enhance the catalytic properties of noble metal catalysts for the solvent-free selective oxidation of benzyl alcohol. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and Brunauer–Emmett–Teller (BET) method. The results clearly showed that the introduced N-containing group prevented the aggregation of graphene sheets and provided more structural defects to maximize the number of exposed active sites. The three-dimensional structure can provide a unique porous structure and large specific surface area. Moreover, the three-dimensional structure makes the recycling and reuse of the catalyst easier. The combination of these properties results in the reduction of the average particle size of metal palladium to 3.2 nm; this significantly increases the catalytic activity of the catalyst. The three-dimensional N-doped graphene aerogel-supported Pd nanoparticle (3D Pd/NRGO) composites exhibit excellent catalytic activity for the solvent-free selective oxidation of benzyl alcohol to benzaldehyde by molecular oxygen at 90 °C for 3 hours under atmospheric pressure, resulting in a 72.2% conversion of benzyl alcohol with 94.5% selectivity for benzaldehyde. In addition, the catalytic efficiency shows no obvious loss even after six repeated cycles. Thus, 3D Pd/NRGO can be used as an efficient, easily separable, recyclable, and stable catalyst for the solvent-free selective oxidation of benzyl alcohol under relatively mild conditions.

3D Pd/NRGO with large surface areas and abundant porous structures was prepared, which served as a novel support to enhance the catalytic properties of noble metal catalysts for the solvent-free selective oxidation of benzyl alcohol.     

Hyperosmolality: another indication for hemodialysis following acute ethylene glycol poisoning

When given early, fomepizole has demonstrated an effective role in the treatment of ethylene glycol (EG) intoxication, often eliminating the need for hemodialysis (HD). Many indications for HD have been suggested for EG intoxication. We present a case of EG intoxication with the second highest reported EG concentration. Despite early treatment with fomepizole and without the development of acidosis or renal insufficiency, the patient required HD for hyperosmolality and subsequent electrolyte imbalances. Indications for HD following EG intoxication are discussed.     

PdPbAg alloy NPs immobilized on reduced graphene oxide/In2O3 composites as highly active electrocatalysts for direct ethylene glycol fuel cells

rGO-modified indium oxide (In₂O₃) anchored PdPbAg nanoalloy composites (PdPbAg@rGO/In₂O₃) were prepared by a facile hydrothermal, annealing and reduction method. Electrochemical tests showed that the as-prepared trimetallic catalyst exhibited excellent electrocatalytic activity and high resistance to CO poisoning compared with commercial Pd/C, mono-Pd and different bimetallic catalysts. Specifically, PdPbAg@rGO/In₂O₃ has the highest forward peak current density of 213.89 mA cm⁻², which is 7.89 times that of Pd/C (27.07 mA cm⁻²). After 3600 s chronoamperometry (CA) test, the retained current density of PdPbAg@rGO/In₂O₃ reaches 78.15% of the initial value. Its excellent electrocatalytic oxidation performance is attributed to the support with large specific surface area and the strong synergistic effect of PdPbAg nanoalloys, which provide a large number of interfaces and achievable reactive sites. In addition, the introduction of rGO into the In₂O₃ matrix contributes to its excellent electron transfer and large specific surface area, which is beneficial to improving the catalytic ability of the catalyst. The study of this novel composite material provides a conceptual and applicable route for the development of advanced high electrochemical performance Pd-based electrocatalysts for direct ethylene glycol fuel cells.

rGO-modified indium oxide (In₂O₃) anchored PdPbAg nanoalloy composites (PdPbAg@rGO/In₂O₃) were prepared by a facile hydrothermal, annealing and reduction method.     

Tailoring the reducibility and catalytic activity of CuO nanoparticles for low temperature CO oxidation

Copper oxide (CuO) nanoparticles have received considerable interest as active and inexpensive catalysts for various gas–solid reactions. The CuO reducibility and surface reactivity are of crucial importance for the high catalytic activity. Herein, we demonstrate that the reducibility and stability of CuO nanoparticles can be controlled and tailored for the high catalytic activity of CO oxidation. The synthesized CuO nanoparticles possessed enhanced reducibility in CO atmosphere at lower reduction temperature of 126 °C compared to 284 °C for that of reference CuO particles. Moreover, the CuO catalysts with tailored reducibility demonstrated a reaction rate of 35 μmol s⁻¹ g⁻¹ and an apparent activation energy of 75 kJ mol⁻¹. Furthermore, the tailored catalysts exhibited excellent long-term stability for CO oxidation for up to 48 h on stream. These readily-reducible CuO nanoparticles could serve as efficient, inexpensive and durable catalysts for CO oxidation at low temperatures.

Copper oxide (CuO) nanoparticles of tailored reducibility could be used as inexpensive, efficient and durable catalysts for CO oxidation at low temperature.     

Promoting formic acid oxidation performance of Pd nanoparticles via Pt and Ru atom mediated surface engineering

The alteration of surface functional properties via incorporation of foreign atoms is supposed to be a key strategy for the enhanced catalytic performance of noble-metal based nanocatalysts (NCs). In the present study, carbon-supported palladium (Pd)-based NCs including Pd, PdPt and PdRuPt have been prepared via a polyol reduction method under the same reduction conditions as for formic acid oxidation reaction (FAOR) applications. By cross-referencing the results of the microscopic, spectroscopic and electrochemical analysis we demonstrated that adding a small amount of platinum (Pt) into Pd NCs (i.e. PdPt NCs) significantly promotes the FAOR performance as compared to that of Pd NCs via weakening the CO^ads bond strength at a lower voltage (0.875 V vs. NHE) than Pd (0.891 V vs. NHE). Of special relevance, the PdPt NC shows a mass activity (MA) of 1.0 A mg⁻¹ and 1.9 A mg⁻¹, respectively, in the anodic and cathodic scan. These values are ∼1.7-fold (0.6 A mg⁻¹) and ∼4.8-fold (0.4 A mg⁻¹) higher than those of Pd NC. Moreover, PdPt NC retains a higher MA (54 mA mg⁻¹) than that of Pd NC (9 mA mg⁻¹) after chronoamperometric (CA) stability tests over 2000 s. Meanwhile, further addition of ruthenium (Ru) (i.e. PdRuPt NCs) outstandingly enhances the CO tolerance during the CA test via removal of adsorbed CO^ads and thus shows the highest MA (62 mA mg⁻¹) after CA testing, which is higher than that of PdPt (54 mA mg⁻¹) and Pd (9 mA mg⁻¹) NCs. The intriguing results obtained in this study have great significance to provide further strategic opportunities for tuning the surface electronic properties of Pd-based NCs to design Pd-based NCs with improved electrochemical performance.

Pt atoms attract electrons from neighboring atoms. Ru atoms attract hydroxide ligands. These two characteristics respectively weaken the bonding and recovering of the Pt site from CO oxidation and then facilitate the FAO in ternary PdPtRu NCs.     

Porous Pt–NiOx nanostructures with ultrasmall building blocks and enhanced electrocatalytic activity for the ethanol oxidation reaction

Oxidized species on surfaces would significantly improve the electrocatalytic activity of Pt-based materials. Constructing three-dimensional porous structures would endow the catalysts with good stability. Here, we report a simple strategy to synthesize porous Pt–NiO_x nanostructures composed of ultrasmall (about 3.0 nm) building blocks in an ethanol–water solvent. Structure and component analysis revealed that the as-prepared material consisted of interconnected Pt nanocrystals and amorphous NiO_x species. The formation mechanism investigation revealed that the preformed amorphous compounds were vital for the construction of porous structure. In the ethanol oxidation reaction, Pt–NiO_x/C exhibited current densities of 0.50 mA cm_Pt⁻² at 0.45 V (vs. SCE), which were 16.7 times higher than that of a commercial Pt/C catalyst. Potentiostatic tests showed that Pt–NiO_x/C had much higher current and better tolerance towards CO poisoning than the Pt/C catalyst under 0.45 V (vs. SCE). In addition, the NiO_x species on the surface also outperformed an alloyed Ni component in the test. These results indicate that the Pt–NiO_x porous nanomaterial is promising for use in direct ethanol fuel cells.

A porous Pt–NiO_x nanomaterial was constructed by a simple strategy to achieve excellent ethanol oxidation catalyst performance.     

Effect of vitamin D3 on the conversion of ethylene glycol to glycolate and oxalate in ethylene glycol-fed rats

Hypercalciuria and hyperoxaluria are important risk factors in the pathogenesis of kidney stones. Urinary glycolate has also been reported to be elevated in patients with renal stones. 1,25-Dihydroxyvitamin D(3), the active metabolite of vitamin D, has been reported to induce hyperoxaluria after either oral or intravenous administration. 1-alpha-D(3), a synthetic derivative of vitamin D, together with ethylene glycol, has been reported to induce renal stones in experimental rats. We have examined the effect of 1-alpha-vitamin D(3) on urinary oxalate and glycolate excretion. Our results indicate that 1-alpha-D(3), together with ethylene glycol, caused a significant increase in urinary glycolate, without a parallel rise in urinary oxalate excretion, in ethylene glycol-fed rats. This increase in urinary glycolate was due to the synergistic effect of both drugs.     

Delayed admission for ethylene glycol poisoning: lack of elevated serum osmol gap

In the absence of an immediately available serum ethylene glycol (EG) assay, the diagnosis of EG poisoning is usually based on anamnesis, clinical findings and presence of metabolic acidosis with elevated serum anion gap, elevated serum osmol gap, hypocalcemia and crystalluria. We report two cases of EG poisoning, both presenting without an elevated serum osmol gap and we discuss conditions which facilitate such a presentation, especially delayed hospital admission. Finally, we confirm the fact that determination of the osmol gap can fail as a screen for EG poisoning. Received: 26 October 1998 Final revision received: 5 March 1999 Accepted: 18 May 1999     

Yttrium stabilization and Pt addition to Pd/ZrO2 catalyst for the oxidation of methane in the presence of ethylene and water

Catalytic oxidation is the most efficient method of minimizing the emissions of harmful pollutants and greenhouse gases. In this study, ZrO₂-supported Pd catalysts are investigated for the catalytic oxidation of methane and ethylene. Pd/Y₂O₃-stabilized ZrO₂ (Pd/YSZ) catalysts show attractive catalytic activity for methane and ethylene oxidation. The ZrO₂ support containing up to 8 mol% Y₂O₃ improves the water resistance and hydrothermal stability of the catalyst. All catalysts are characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), O₂-temperature-programmed desorption (O₂-TPD), and CO-chemisorption techniques. It shows that high Pd dispersion and Pd–PdO reciprocation on the Pd/YSZ catalyst results in relatively high stability. In situ diffuse reflectance infrared Fourier-transform (DRIFT) experiments are performed to study the reaction over the surface of the catalyst. Compared with bimetallic catalysts (Pd : Pt), the same amounts of Pd and Pt supported on ZrO₂ and Y₂O₃-stabilized ZrO₂ catalysts show enhanced activity for methane and ethylene oxidation, respectively. A mixed hydrocarbon feed, containing methane and ethylene, lowers the CH₄ light-off temperature by approximately 80 °C. This shows that ethylene addition has a promotional effect on the light-off temperature of methane.

Addition of 8.0% Yttrium (Y) to ZrO₂ substantially increased the activity and stability of Pd/ZrO₂.     

Poly(lactic acid)-poly(ethylene glycol) nanoparticles as new carriers for the delivery of plasmid DNA.

The purpose of the present work was to produce and characterize poly(lactic acid)-poly(ethylene glycol) (PLA-PEG) nanoparticles (size lower than 300 nm) containing a high loading of plasmid DNA in a free form or co-encapsulated with either poly(vinyl alcohol) (PVA) or poly(vinylpyrrolidone) (PVP). The plasmid alone or with PVA or PVP was encapsulated by two different techniques: an optimized w/o/w emulsion-solvent evaporation technique as well as by a new w/o emulsion-solvent diffusion technique. Particle size, zeta potential, plasmid DNA loading and in vitro release were determined for the three plasmid-loaded formulations. The influence of the initial plasmid loadings (5, 10, 20 microg plasmid DNA/mg PLA-PEG) on those parameters was also investigated. The plasmid loaded into the nanoparticles and released in vitro was quantified by fluorimetry and the different molecular forms were identified by gel electrophoresis. PLA-PEG nanoparticles containing plasmid DNA in a free form or co-encapsulated with PVA or PVP were obtained in the range size of 150-300 nm and with a negative zeta potential, both parameters being affected by the preparation technique. Encapsulation efficiencies were high irrespective of the presence of PVA or PVP (60-90%) and were slightly affected by the preparation technique and by the initial loading. The final plasmid DNA loading in the nanoparticles was up to 10-12 microg plasmid DNA/mg polymer. Plasmid DNA release kinetics varied depending on the plasmid incorporation technique: nanoparticles prepared by the w/o diffusion technique released their content rapidly whereas those obtained by the w/o/w showed an initial burst followed by a slow release for at least 28 days. No significant influence of the plasmid DNA loading and of the co-encapsulation of PVP or PVA on the in vitro release rate was observed. In all cases the conversion of the supercoiled form to the open circular and linear forms was detected. In conclusion, plasmid DNA can be very efficiently encapsulated, either in a free form or in combination with PVP and PVA, into PLA-PEG nanoparticles. Additionally, depending on the processing conditions, these nanoparticles release plasmid DNA either very rapidly or in a controlled manner.     

Poly(ethylene glycol)-avidin bioconjugates: suitable candidates for tumor pretargeting.

Avidin-poly(ethylene glycol) (PEG) conjugates were obtained by derivatization of about 10% of the protein amino groups (four amino groups per protein molecule) with linear 5 kDa PEG or branched 10 or 20 kDa PEGs. Circular dichroism analysis showed that the polymer conjugation neither altered the protein structure nor the environment of the aromatic amino acids which are present at the level of the biotin binding site. Spectroscopic studies were carried out to evaluate the biotin recognition activity of the conjugates either in terms of number of biotin binding sites or avidin/biotin affinity. Avidin-PEG 5 kDa and avidin-PEG 10 kDa displayed over 90% of the native protein biological activity while a reduction in the recognition of biotinylated antibodies of about 25% was found with PEG 20 kDa. In vivo studies demonstrated that the protein immunogenicity was in the order: wild type avidin>avidin-PEG 5 kDa>avidin-PEG 10 kDa>avidin-PEG 20 kDa. By intravenous injection into mice bearing a solid tumor, all conjugates displayed prolonged permanence in the circulation with respect to the native protein. The area under the curve values of avidin-PEG 5 kDa, avidin-PEG 10 kDa and avidin-PEG 20 kDa were about 3-, 7- and 30-times higher than the wild type avidin with reduced accumulation in kidneys and liver. Interestingly, all conjugates accumulated significantly in the tumor mass. In particular, in the case of avidin-PEG 20 kDa, 8% of the injected dose (ID)/g of tissue accumulated in the tumor after 5 h from the administration and over 6% of the ID/g was maintained throughout 72 h.     

Massive ethylene glycol poisoning without evidence of crystalluria: a case for early intervention

A case of severe ethylene glycol poisoning is presented, characterized by protracted delirium, coma, and delayed adult respiratory distress syndrome. This patient never demonstrated evidence of calcium oxalate crystalluria or renal insufficiency. Ethylene glycol intoxication should be considered in the patient who presents with an altered mental status, unexplained metabolic acidosis, and elevated anion and osmolal gaps with or without crystalluria. Early empiric ethanol therapy and consideration of dialysis are recommended for those patients with such a presentation without evidence of abnormal levels of ketones, lactate, salicylate, or ethanol. It is proposed that early ethanol therapy may prevent the formation of ethylene glycol metabolites to the extent that calcium oxalate crystalluria is not seen.     

Antitumor activity of poly(ethylene glycol)-camptothecin conjugate: the inhibition of tumor growth in vivo.

Antitumor effect of poly(ethylene glycol)-camptothecin conjugate (PEG-CPT) was studied in the nude mouse model of human colon cancer xenografts. The animals were treated intravenously with 15 mg/kg of camptothecin (CPT) or PEG-CPT conjugate at equivalent CPT dose. Antitumor activity, apoptosis induction and caspase-dependent signaling pathways were studied 12, 24, 48 and 96 h after single injection. In addition, pharmacokinetics, tumor distribution and accumulation of PEG polymer labeled with green fluorescence protein (GFP) were studied. The data obtained showed that the conjugation of low molecular weight anticancer drug CPT with low solubility to high molecular weight water-soluble PEG polymer provides several advantages over the native drug. First, the conjugation improves drug pharmacokinetics in the blood and tumor. Second, such conjugation provides passive tumor targeting by the Enhanced Permeability and Retention (EPR) effect, increasing drug concentration in the tumor. Third, the coupling increases the bioavailability of CPT, induces apoptosis in tumor and, therefore, enhances anticancer activity of PEG-CPT. Thus, the use of macromolecular conjugate provided passive tumor targeting of the drug, improved pharmacokinetics and increased the stability of the drug during circulation. It offered better uptake by the targeted tumor cells and substantially enhanced apoptosis and antitumor activity of the conjugated drug in the tumor and decreased apoptosis in liver and kidney as compared with the native drug. All these characteristics make PEG-CPT conjugate an attractive anticancer drug for the effective chemotherapy of solid tumors.     

Methanol and ethylene glycol poisoning: a case study and review of current literature

Poisoning is an uncommon but potentially fatal outcome of toxic alcohol ingestion. The toxic alcohols methanol, ethylene glycol and isopropyl alcohol are commonly found in household and commercial products. Because the toxic effects are caused by the metabolites of methanol and ethylene glycol rather than the agents themselves, there is often a substantial delay between ingestion and onset of clinical toxicity. Anion and osmolar gaps are often used for the diagnosis and exclusion of these sometimes subtle overdoses. The pitfalls of using these tests to rule out alcohol ingestion are reviewed. Ethanol infusion is the traditional therapy for such overdoses. In addition to the pathophysiology and clinical findings in poisoning, recent evidence for the use of fomepizole and adjuvant therapies is reviewed.     

Microwave-assisted synthesis of octahedral Rh nanocrystals and their performance for electrocatalytic oxidation of formic acid

Uniform and well-defined octahedral Rh nanocrystals were rapidly synthesized in a domestic microwave oven for only 140 s of irradiation by reducing Rh(acac)₃ with tetraethylene glycol (TEG) as both a solvent and a reducing agent in the presence of an appropriate amount of KI, didecyl dimethyl ammonium chloride (DDAC), ethylene diamine (EDA) and polyvinylpyrrolidone (PVP). KI, DDAC and EDA were essential for the creation of octahedral Rh nanocrystals. Electrochemical measurements showed a significantly enhanced electrocatalytic activity and stability for the as-prepared octahedral Rh nanocrystals compared with commercial Rh black.

Octahedral Rh nanocrystals were rapidly synthesized in a domestic microwave oven for only 140 s of irradiation by reducing Rh(acac)₃ with tetraethylene glycol as both a solvent and a reducing agent.

To date, platinum group metals play an indispensable role as efficient catalysts for some important reactions in industry. However, due to their limited reserves and high prices, a large number of platinum group metal nanoparticles with different particle sizes, morphologies and surface structures have been synthesized by means of various methods to reduce their cost.¹ As a platinum group metal, Rh has good catalytic activity and stability, and is often used as a typical catalyst for some chemical reactions such as hydrogenation,^2–7 nitrogen oxide reduction,⁸ CO oxidation,^9–11 cross coupling,^12–14 hydroformylation,^15–19 in fuel cells^20,21 and other chemical reactions.²² Therefore, controlled syntheses of Rh nanoparticles with different morphologies have attracted much attention. In recent years, people have successfully prepared Rh nanostructures with various morphologies such as sheet,^23–27 flower,⁶ polyhedron,^28–33 porous ball,⁸ multi branches,^34–39 stars,⁴⁰ nanoframes^13,14,41 and nano nail.⁴² These Rh nanoparticles with unique structures effectively improve the atom utilization as well as their catalytic reaction performances. However, similar to other platinum group metals, the difficulty of large-scale preparation of Rh nanomaterials with single morphology and uniform size still greatly restricts their industrial application.Microwave irradiation has been widely used in chemical synthesis because of its simple, rapid and efficient characteristics as well as special heating mode from the inner. We have synthesized many metallic nanoparticles with different shapes by using microwave irradiation for about 80 to 120 seconds. Herein, we report a simple and fast strategy for the synthesis of octahedral Rh nanocrystals under microwave irradiation with using domestic microwave oven. In a typical synthesis, octahedral Rh nanocrystals with uniform and well-defined morphologies were successfully synthesized with Rh(acac)₃ as the precursor, polyvinyl pyrrolidone (PVP) as the stabilizer, triethylene glycol (TEG) as both a solvent and a reducing agent in the presence of didecyl dimethyl ammonium chloride (DDAC), KI and ethylene diamine (EDA) under microwave irradiation in a very short time. Meanwhile, the electrocatalytical performance of the as-prepared octahedral Rh nanocrystals for the electro-oxidation of formic acid was also investigated with commercial Rh black as a contrast.The TEM and SEM images of the representative Rh nanoparticles obtained under the optimal experimental conditions are shown in Fig. 1, S1 and S2.^† Wherein, the prepared Rh nanoparticles demonstrated uniform and well-defined octahedral structure with sharp edges and corners as well as smooth surfaces (Fig. 1a and b), in which the average side length is about 65 nm. The high-resolution TEM (HRTEM) image (Fig. 1c) shows well-resolved continuous fringes clearly. The corresponding fast Fourier transform (FFT) pattern, as the inset shown in Fig. 1c, shows a lattice distance of 0.194 or 0.216 nm, which can be attributed to the {200} and {111} lattice planes of the octahedral Rh with face-centered cubic structure, respectively, confirming its single-crystal nature. Furthermore, the regular octahedral feature of the as-prepared Rh nanoparticles can be well distinguished from SEM images, as shown in Fig. 1d and S2.^† These results show that the octahedral Rh nanocrystals with a single morphology can be rapidly synthesized in a great quantity by irradiation with domestic microwave oven for only 140 s.Open in a separate windowFig. 1TEM and SEM images of the as-prepared octahedral Rh nanocrystals. (a) and (b) Typical TEM images with different scales. The inset in (b) is the schematic illustration; (c) typical HRTEM image. The inset is the corresponding FFT pattern; (d) SEM image. Fig. 2a shows the XRD pattern of the as-prepared typical octahedral Rh nanocrystals. As can be seen, the diffraction peaks at 2θ values of 41.26, 47.95, 70.18 and 84.33° are observed, which can be well indexed to the diffractions of (111), (200), (220) and (311) lattice facets of metallic Rh referring to the standard powder diffraction card (JCPDS card No. 05-0685), respectively. This observation further confirmed their fcc Rh structure. In addition, the narrow and sharp (111) diffraction peak implied that the typical octahedral Rh nanocrystals exhibited a high purity and crystallinity. The XPS spectrum was taken for the as-prepared octahedral Rh nanocrystals and the result was displayed in Fig. 2b, As it can be seen, two peaks corresponding to the electron binding energies of Rh 3d_3/2 and Rh 3d_5/2 were observed at 311.85 eV and 307.10 eV with an interval of 4.75 eV, respectively, which were consistent with the literature values (311.75 and 307.0 eV),⁴³ revealing Rh(0) metallic state of the octahedral nanocrystals.Open in a separate windowFig. 2XRD pattern (a) and XPS spectrogram (b) of octahedral Rh nanocrystals.The dependence of the morphological evolution of Rh nanocrystals upon irradiation time was investigated. When irradiated for 120 s, the octahedral structural Rh nanocrystals with about 65 nm of the side length produced except for unclear edges and corners as well as a shorter side length, as shown in Fig. 3a. As microwave irradiation progressed to 140 s, uniform and well-defined octahedral Rh nanocrystals with smooth surfaces generated (Fig. 3b). While the irradiation time was extended to 160 s, however, the vertices of some octahedral structures were truncated although with no change of the sizes, as shown in Fig. 3c. As the irradiation time reached 180 s, the octahedral structural feature of most particles disappeared with a further truncation of their vertices (Fig. 3d), which should be ascribed to higher surface free energies for the metallic atoms at the apexes and edges as well as a higher internal temperature due to a longer irradiation time. These results indicated that the optimum microwave irradiation time was 140 s for the creation of regular octahedral Rh nanocrystals.Open in a separate windowFig. 3TEM images of Rh nanoparticles prepared at different reaction time. (a) 120 s; (b) 140 s; (c) 160 s; (d) 180 s.It was noteworthy that KI played a crucial role in controlling synthesis of octahedral Rh nanocrystals. When no KI was used, it would produce irregular Rh nanoparticles, as shown in Fig. 4a. While with addition of 0.6 mmol of KI, octahedral Rh nanostructures with blunt vertices and an average side length of about 50 nm were generated (Fig. 4b), implying an incomplete growth relative to the case of 0.8 mmol of KI as in the typical experimental process (Fig. 1). Nevertheless, the amount of KI was increased to 1.2 mmol, only less octahedral structure features could be observed except for few obscure polyhedral outlines (Fig. 4c). These results indicated that the existence of KI was advantageous to the generation of octahedral Rh nanocrystals. Generally, the eight triangular surfaces of metallic Rh octahedron consists of (111) lattice planes. According to the previous report,^44–49 it can be considered that the preferential adsorption of I⁻ anions on Rh (111) planes is one of the main factors driving the formation of octahedral structure. As a result, a growth along 〈111〉 directions was confined and a growth along 〈100〉 directions was facilitated, which created octahedral structures due to anisotropic growth. However, excessive I⁻ ions would adsorb non-selectively on the surfaces of Rh nanoparticles, which resulted in passivation of the edges and corners of polyhedron. In addition, an equivalent amount of KBr or KCl was used instead of KI, respectively, to clarify the role of I⁻ ions under the same other conditions. As can be seen (Fig. S3, ESI^†), no octahedral Rh nanocrystal except for agglomerated irregular nanosheets was observed in these two contrast experiments. This may be ascribed to the change of the precursor. In the presence of a large number of I⁻ ions, the precursor can be transformed to a more stable [RhI₆]³⁻ complex.^44–47 As a result, the reducing rate of Rh(iii) to Rh atom decreased, which may be favourable for the nucleation of Rh nanoparticles and the oriented growth of Rh octahedra.Open in a separate windowFig. 4TEM images of Rh nanoparticles prepared with different amounts of DDAC or KI under the same other conditions. (a) Absence of KI; (b) 0.6 mmol of KI; (c) 1.2 mmol of KI; (d) absence of DDAC; (e) 0.2 mmol of DDAC; (f) 0.6 mmol of DDAC.Meanwhile, the influence of DDAC on the generation of octahedral Rh nanocrystals was also studied under the same other conditions. In the absence of DDAC, only agglomerated irregular Rh nanoparticles were observed (Fig. 4d). When 0.2 mmol of DDAC was added, octahedral Rh nanostructures with an average side length of about 45 nm, a smaller size relative to the case of 0.4 mmol of DDAC as in the typical experiments (Fig. 1), were generated accompanying with a few irregular nanoparticles (Fig. 4e). With increasing the amount of DDAC to 0.6 mmol, agglomerated irregular polyhedral nanostructures formed (Fig. 4f). Thus, the addition of DDAC was also indispensable for the growth of octahedral Rh nanostructures under microwave irradiation. Whereas an excessive amount of DDAC was also unfavourable for creation of the octahedral Rh nanocrystals. Moreover, no octahedral nanostructures generated except for urchin-like Rh hierarchical superstructures when adding an equivalent amount of cetyltrimethylammonium chloride (CTAC) instead of DDAC (Fig. S4a, ESI^†). While didoctyl dimethyl ammonium bromide (DDAB) was used instead of DDAC, the formation of octahedral Rh structures can be still observed although accompanying with other irregular polyhedral (Fig. S4b, ESI^†). These results suggested that the formation of octahedral Rh nanostructures were strongly dependent upon the hydrophobic chains of DDAC or DDAB but nothing to do with Cl⁻ or Br⁻ anions. The effect of other halide ions can be ignored due to the existence of a large number of I⁻ ions. That is because the strength of adsorption of I⁻ ions on metal surfaces is generally stronger than that of Cl⁻ or Br⁻ ions.⁴⁸Accordingly, the generation of octahedral Rh nanocrystals should be ascribed to the synergistic effect of KI and DDAC under the above experimental conditions. We believe that DDAC could enhance the role of I⁻ ions in generating (111) facets of octahedral by adjusting the adsorption selectivity of I⁻ ions on (111), (100) or (110) facets. On the one hand, the amount of KI would manipulate the reducing kinetics to form octahedral Rh nanostructures under microwave irradiation. A slow reducing rate was favourable for the oriented growth of Rh octahedra due to the formation of a more stable coordinated anion [RhI₆]³⁻. On the other hand, the confinement of DDAC induced the selective adsorption of I⁻ ions on Rh {111} facets which restrained the growth along 〈111〉 directions of Rh nuclei and prompted the growth along 〈100〉 directions. In addition, a proper quantity of DDAC confined the deposition of Rh atoms on {111} facets, which may be beneficial to the growth along 〈100〉 directions. However, an excessive amount of DDAC was unfavourable for the formation of shaped Rh nanoparticles since they disturbed the adsorption of I⁻ anions on Rh {111} facets.Furthermore, it was also found that ethylene diamine (EDA) demonstrated an important effect on the creation of octahedral Rh nanostructures. Under keeping the total volume of the reaction system unchanged, the significantly agglomerated irregular polyhedral nanoparticles with sharp horns were observed in absence of EDA (Fig. S5a^†). When 0.5 mL of EDA was added, a few octahedral nanostructures began to generate though accompanying with agglomerated irregular polyhedra (Fig. S5b^†). While the amount of EDA was increased to 1 mL, uniform and well-defined octahedral Rh nanocrystals with flat and smooth surfaces were produced (Fig. S5c^†). However, a more amount of EDA was added, a part of octahedral nanostructures become deformation as well as agglomeration (Fig. S5d^†). In the reaction system, TEG as a solvent was also served as a reducing agent. As can be seen, even though without adding EDA, the rhodium salt was still reduced completely to produce metal Rh nanoparticles. With the addition of EDA, octahedral Rh nanocrystals began to generate, while an excessive amount of EDA resulted in unclear edges and corners of the octahedral structures. Obviously, EDA demonstrated significant effect on the morphology control of octahedral Rh nanocrystals. It should be ascribed to the coordination adsorption of EDA on the surface of metal particles.⁵⁰ Furthermore, no octahedral nanostructures but irregular nanoparticles or Rh dendrites generated with using an equivalent amount of n-butylamine or n-octylamine instead of EDA (Fig. S6a and b^†). Therefore, we suggest that EDA plays a synergistic role together with DDAC in regulating the rate of atomic packing and nanoparticle growth by coordination adsorption. The growth rate of nanoparticles is faster in absence of EDA, while the growth rate slows down with the increase of EDA dosage. An appropriate amount of EDA facilitates the generation of uniform octahedral Rh nanocrystals by adjusting the balance between nucleation rate and growth rate. Nevertheless, excessive EDA makes a slower growth than nucleation due to their extreme adsorption, resulting in obscure appearances of some octahedral Rh nanoparticles.In addition, PVP was also found to be important but not essential for the formation of octahedral Rh nanocrystals. Either without or with a few amount of PVP, octahedral Rh nanocrystals can also produce except for a little agglomeration (Fig. S7a and b^†). An appropriate amount of PVP contributed to uniform and well dispersed octahedral Rh nanocrystals, while excessive PVP caused aggregation (Fig. S7c and d^†). These results indicated that PVP served mainly as a protecting and dispersing agent for the nanocrystals.The catalytic performance of the synthesized octahedral Rh nanocrystals was tested by cyclic voltammetry (CV) and chronoamperometry (CA) with the formic acid electrooxidation reaction as the model reaction system. Fig. 5a exhibits the representative CV curves obtained for the electrochemical oxidation of 0.5 mol L⁻¹ HCOOH over the octahedral Rh nanocrystals and commercial Rh black in 0.5 mol L⁻¹ HClO₄ solution, respectively. CV measurements showed the peak current density for the octahedral Rh nanocrystals was 3.53 mA cm⁻² at 0.544 V, while it was 1.01 mA cm⁻² at 0.609 V for Rh black. The formic acid electrooxidation indicated that the electrocatalytic activity of octahedral Rh nanocrystals was about 3.5 times that of Rh black, demonstrating an obvious morphological dependence for their electrochemical property. The corresponding CA curves of formic acid electro-oxidation at 0.55 V is shown in Fig. 5b. As can be seen, a higher current retention through the whole measuring range were observed over the as-prepared octahedral Rh nanocrystals than Rh black though both of them showed an equivalent attenuation rate in the initial 20 seconds. The CV curve of continuous cycle scanning for octahedral Rh nanocrystals in 0.5 mol L⁻¹ HClO₄ solution showed a decrease of the electrochemical activity only by 9.6% after 2000 cycles (Fig. S8^†). These results reveal that octahedral Rh nanocrystals exhibit a remarkably enhanced electrochemical activity and stability compared with Rh black. Their enhanced catalytic activity should be attributed to the uniform geometric structure with single surface lattice.Open in a separate windowFig. 5The CV (a) and CA (b) curves for the electrochemical oxidation of 0.5 mol L⁻¹ HCOOH over the octahedral Rh nanocrystals and Rh black in 0.5 mol L⁻¹ HClO₄ solution, respectively.Additionally, CO stripping voltammetry measurements were performed. As shown in Fig. S9a,^† no CO electro-oxidation (CO_ox) was observed for the freshly-prepared octahedral Rh nanocrystals in 0.5 M HClO₄ solution. Subsequently, a current peak for CO_ox appeared at 0.550 V (versus SCE) after adorbing CO for the clean octahedral Rh-modified electrode, as shown in Fig. S9b.^† Then CO_ox peak disappeared in the following second potential scanning, as shown in Fig. S9c.^† These results showed that CO adsorbed on Rh surfaces can be easily removed in the process of electrocatalytic oxidation, showing well CO resistence.In summary, uniform octahedral Rh nanocrystals could be rapidly prepared with domestic microwave oven in only 140 s of irradiation by reducing Rh(acac)₃ with TEG as both a solvent and a reducing agent, PVP as a protecting and dispersing agent in the presence of proper quantities of DDAC, KI and EDA. The formation of octahedral Rh nanocrystals was attributed to the synergism of KI, DDAC and EDA. The electrochemical oxidation of formic acid demonstrated higher electrocatalytic activity and stability for the as-prepared octahedral Rh nanocrystals than Rh black, displaying a significant dependence upon their morphologies.     

Palladium nanoparticles loaded on nitrogen and boron dual-doped single-wall carbon nanohorns with high electrocatalytic activity in the oxygen reduction reaction

Palladium nanoparticles with a diameter of 2–4 nm supported on nitrogen and boron dual-doped single-wall carbon nanohorns (Pd-NBCNHs) are synthesized via a one-step method and their electrocatalytic activities are investigated for the oxygen reduction reaction (ORR) in alkaline media. The electrochemical results demonstrate that the oxygen reduction peak potential of Pd-NBCNHs is similar to that of commercial 20% Pt–C. Furthermore, Pd-NBCNHs show a more positive half-wave potential than 20% Pt–C and display better long-term stability and resistance to methanol than 20% Pt–C, which is attributed to the synergetic effect of the Pd nanoparticles and NBCNHs. As NBCNHs have abundant pyrrolic nitrogen, charged sites and defective structures, they not only act as a carrier, but also provide the active sites for oxygen adsorption during the oxygen reduction reaction process. The outstanding electrochemical performance makes Pd-NBCNHs promising to be applied in fuel cells.

Palladium nanoparticles with a diameter of 2–4 nm loaded on nitrogen and boron dual-doped single-wall carbon nanohorns (Pd-NBCNHs) are prepared via one-step method and their electrocatalytic activities are studied for the oxygen reduction reaction.