Pt-Me (Me = Ir, Ru, Ni) binary alloys as an ammonia oxidation anode

Various Pt-Me (Me = Ir, Ru or Ni) binary alloys were prepared on a glassy carbon (GC) substrate by thermal decomposition and compared as the electrocatalyst for ammonia oxidation in KOH solutions. On the solid solutions of Pt_1−xIr_x (0≤x≤1.0) and Pt_1−xRu_x (0≤x≤0.6), ammonia oxidation was found to begin at a lower potential (−0.6 V versus Ag/AgCl) than on pure Pt by about 0.1 V. During potentiostatic oxidation the current density j decreased considerably within about 300 s. The arbitrarily selected j₆₀ (j after 60 s) tended to saturate at a high set potential region probably due to the deactivation by a poison of N_ads. The saturated j₆₀ at a high oxidation potential was apparently higher on Pt_1−xIr_x (x≤0.8) or Pt_1−xRu_x (x≤0.4) than on Pt, which suggested a positive cooperation of Ir and Ru with Pt in the electrocatalysis. On the other hand, Ni added as a solute to Pt contributed to lower j₆₀ with x in Pt_1−xNi_x (0≤x≤0.7) and did not lower the starting potential of ammonia oxidation at all. The reason why Ir and Ru enhance the activity might be explained by their activity at the dehydrogenatation steps of NH₃ at a lower potential, at which ammonia oxidation can never start on the surface of pure Pt.     

Investigation on modification of Ru/CNTs catalyst for the generation of COx-free hydrogen from ammonia

The modification of Ru/CNTs (CNTs denotes carbon nanotubes) with rare earth, alkali, and alkaline earth compounds were systematically studied. The loading of modifying agents leads to decrease in pore volume and surface area; but improvement in thermal stability of Ru/CNTs. The size and morphology of Ru particles are not affected by the modification. For the catalysts modified by metal nitrates, activities were found in the order of K–Ru>Na–Ru>Li–Ru>Ce–Ru>Ba–Ru>La–Ru>Ca–Ru>Ru, signifying that within the same groups (K, Na and Li; Ba and Ca), the higher the electronegativity of the promoter, the lower is the NH₃ conversion. Of all the potassium salts adopted, KNO₃, KOH, and KCO₃ show similar promotional effect, suggesting that KOH is the active promoter for catalytic activity. The maximum promotional effect was observed at an atomic ratio of K/Ru=2. The electron-withdrawing groups, F⁻¹, Cl⁻¹, Br⁻¹, SO₄²⁻, and PO₄³⁻ are inhibitors of Ru catalysts. The results of N₂-TPD investigation revealed that the promotional effects of a modifier is a combined result of: (i) enhancing combinative desorption of nitrogen atoms, and (ii) decreasing of the apparent activation energy of the decomposition reaction.     

Scanning electrochemical microscopy characterization of bimetallic Pt–M (M = Pd, Ru, Ir) catalysts for hydrogen oxidation

A combinatorial screening method, combined with scanning electrochemical microscopy (SECM) in a tip-generation–substrate-collection (TG–SC) mode, was applied to systematically and rapidly identify potential bimetallic catalysts (Pt–M, M = Pd, Ru, Ir) for the hydrogen oxidation reaction (HOR). The catalytic oxidation of hydrogen on the candidate catalysts was further examined during cyclic voltammetric scans of the substrate with a tip close to the substrate. The quantitative rate of hydrogen oxidation on the candidate substrates was determined for different substrate potentials from SECM approach curves by fitting to a theoretical model. SECM screening results revealed that Pt₄Pd₆, Pt₉Ru₁ and Pt₃Ir₇ were the optimum composition of the catalysts from the Pt–Pd, Pt–Ru and Pt–Ir bimetallic systems for hydrogen sensors. The catalytic activity of the candidate catalysts in HOR was highly dependent on the substrate potential. The kinetic parameters for HOR were obtained on Pt₄Pd₆ (Tafel slope = 124 mV, k° = 0.19 cm/s, α = 0.52), Pt₉Ru₁ (Tafel slope = 140 mV, k° = 0.08 cm/s, α = 0.58) and Pt₃Ir₇ (Tafel slope = 114 mV, k° = 0.11 cm/s, α = 0.48) and compared with Pt (Tafel slope = 118 mV, k° = 0.17 cm/s, α = 0.5). Among the bimetallic catalysts studied, Pt₄Pd₆ exhibited the highest activity toward HOR with a high standard rate constant value in a wide range of applied potentials.     

The active phase of Au–Pd/Al2O3 for CO oxidation

Au–Pd/Al₂O₃ catalyst was prepared by modified impregnation method. It was found that the catalyst calcined in air at 473 K showed higher CO oxidation activity in comparison with the catalysts treated at other temperature. Nitrogen adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure spectroscopy (XANES) techniques were employed to study the relationship between the surface/bulk structures of these catalysts and their catalytic performance. The results indicated the higher activity was attributed to the smaller pore volume and co-existence of PdO and Au⁰ in their surface. The formation of Au_xPd_y alloy was unfavorable for the catalytic reaction.     

Selective reduction of NO with CO in the presence of O2 with Ir/WO3 catalysts: Influence of preparation variables on the catalytic performance

Several Ir/WO₃ catalysts were prepared, which were different in the loading of Ir (up to 10 wt.%) and in the pretreatment conditions, and used for the reduction of NO (500 ppm) with CO (3000 ppm) in the presence of excess O₂ (5%), SO₂ (2 ppm), and H₂O (1%). The rate of NO conversion per unit mole of Ir was found to be maximal at a small Ir loading of 0.5–1.0 wt.%. The good catalytic performance was achieved when the Ir precursors (IrO_x) supported on WO₃ were reduced under mild conditions by He at 400 °C or H₂/He at a lower temperature of 130 °C. The catalysts were characterized by XRD, FTIR after CO adsorption, and H₂-TPR. The characterization results show that the active sites are exposed zero-valent Ir species, in accordance with previous works using Ir on WO₃ and other supports, and that the fraction of these active species is larger for a higher degree of Ir dispersion (smaller Ir particles). The preparation conditions for highly active Ir/WO₃ catalysts were confirmed and possible reaction mechanisms were discussed.     

Electrochemical properties of electrospun CuxO (x = 1, 2)-embedded carbon nanofiber with EXAFS analysis

The Cu_xO (x = 1, 2)-embedded carbon nanofibers (Cu_xO/CNF) were prepared by electrospinning of the composite solutions of Cu(II) acetate, PAN (polyacrylonitrile) and PVP (polyvinylpyrrolidone), and subsequent stabilization and carbonization. The structure of Cu₂O/CNF is largely dependent on the carbonization temperature. The Cu_xO/CNF-700 has the disordered CuO structure, while the Cu_xO/CNF-800 has the intermediate structure between the disordered CuO and Cu₂O. The structural change in the CNF prepared by electrospinning and optimum thermal treatment leads to excellent electrochemical properties. The CNF plays an important role as buffering agent to prevent Cu_xO particles from agglomerating. Besides, the aligned CNF with high electrical conductivity leads to the occurrence of Cu nano-particles in the discharging process, and it serves to convert Li₂O into Li in the charging process. Both Cu_xO/CNF-700 and Cu_xO/CNF-800 exhibit high specific discharge capacity, exceptional cycle retention, and excellent reversible capacity even in initial cycle, while Cu_xO/CNF-900 shows bad electrochemical performance.     

Methanol oxidation on carbon-supported Pt-Ru and TiO2 (Pt-Ru/TiO2/C) electrocatalyst prepared using polygonal barrel-sputtering method

Methanol oxidation performance of a carbon-supported Pt-Ru alloy catalyst used at the direct methanol fuel cell (DMFC) anode is improved by adding TiO₂. However, the methanol oxidation performance of the electrocatalyst described above must be enhanced further to realize practical application in DMFCs. In this study, we used our original surface-modifying technique termed the “polygonal barrel-sputtering method” to prepare a carbon-supported Pt-Ru and TiO₂ (Pt-Ru/TiO₂/C) electrocatalyst offering higher methanol oxidation performance. The obtained results show that the methanol oxidation performance of the prepared Pt-Ru/TiO₂/C is superior to that using wet process as the TiO₂ deposition method. Furthermore, for our sputtering method, the peak current of methanol oxidation on the Pt-Ru/TiO₂/C is enhanced by increasing the TiO₂ deposited amount up to 2.8 wt.%. These results suggest that a Pt-Ru/TiO₂ interface area is increased using the polygonal barrel-sputtering method, providing the high methanol oxidation performance of Pt-Ru/TiO₂/C.     

Electrochemical oxidation of ammonia (NH4/NH3) on thermally and electrochemically prepared IrO2 electrodes

The electrochemical oxidation of ammonia (NH₄⁺/NH₃) in sodium perchlorate was investigated on IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor and the anodic oxidation of metallic iridium. The electrochemical behaviour of Ir(IV)/Ir(III) surface redox couple differs between the electrodes indicating that on the anodic iridium oxide film (AIROF) both, the surface and the interior of the electrode are electrochemically active whereas on the thermally decomposed iridium oxide films (TDIROF), mainly the electrode surface participates in the electrochemical processes.On both electrodes, ammonia is oxidized in the potential region of Ir(V)/Ir(IV) surface redox couple activity, thus, may involve Ir(V). During ammonia oxidation, TDIROF is deactivated, probably by adsorbed products of ammonia oxidation. To regenerate TDIROF, it is necessary to polarize the electrode in the hydrogen evolution region. On the contrary, AIROF seems not to be blocked during ammonia oxidation indicating its fast regeneration during the potential scan. The difference between both electrodes results from the difference in the activity of the iridium oxide surface redox couples.     

Influence of BaO on Pd/Al2O3-based catalysts in C2H4 and CO oxidation as well as in NO reduction

In this study, Pd/Al₂O₃ and Pd/BaO/Al₂O₃ metallic monoliths were used to investigate the effect of BaO in C₂H₄ and CO oxidation as well as in NO reduction. A FT-IR gas analyser was used to study the activity of the catalysts. Several activity experiments carried out with dissimilar feedstreams revealed that BaO enhances CO and C₂H₄ oxidation as well as NO reduction reactions in rich conditions. This effect is due to BaO, which causes a decrease in the ethene poisoning of palladium. In lean conditions BaO is present in the form of Ba(OH)₂ which reacts with oxidised NO releasing water. Therefore, NO was stored during the lean reaction.     

An IR study of thermally stable V2O5-WO3 -TiO2 SCR catalysts modified with silica and rare-earths (Ce, Tb, Er)

The catalytic activity of silica-free and silica-modified rare earth (Ce, Tb, Er) containing V₂O₅-WO₃ -TiO₂ catalysts in the selective catalytic reduction of NO by ammonia has been investigated as a function of ageing temperatures. The adsorption of ammonia on the catalysts and the behavior of their surface hydroxy groups and of bulk vibrations has also been studied by IR spectroscopy. Rare earths slightly decrease the catalytic activity of catalysts in a fresh state, and this has been attributed to the perturbation, observed by IR, of the vanadyl groups with a likely lowering of their Lewis acidity. However, rare earths (in particular Tb and Er) increase strongly the catalytic activity of catalysts after ageing. Silica only does not seem to have a positive effect on thermal stability and activity when vanadium is present. It has been concluded that rare earths strongly increase the thermal resistance of the catalysts and inhibit rutilization and surface area loss because they do not penetrate the anatase bulk while tend to cover the external surface. In addition the negative action of free vanadium on phase stability is decreased due to formation of rare earth vanadates.     

Synthesis, characterization and performance of CuO/La2O3 composite catalyst for ammonia catalytic oxidation

This work considers the oxidation of ammonia (NH₃) by selective catalytic oxidation (SCO) over a CuO/La₂O₃ composite catalyst at temperatures between 150 and 400 °C. A CuO/La₂O₃ composite catalyst was prepared by co-precipitation of copper nitrate and lanthanum nitrate at various molar concentrations. This study also considers how the concentration of influent NH₃ (C₀ = 1000 ppm), the space velocity (GHSV = 92,000 l/h), the relative humidity (RH = 12%) and the concentration of oxygen (O₂ = 4%) affect the operational stability and the capacity for removing NH₃. The catalysts that were characterized using FTIR, XRD, UV-Vis, BET and PSA, have shown that the catalytic behavior is related to the copper (II) oxide, while lanthanum (III) oxide may serve only to provide active sites for the reaction during a catalyzed oxidation run. The experimental results show that the extent of conversion of ammonia by SCO in the presence of the CuO/La₂O₃ composite catalyst was a function of the molar ratio. The ammonia was removed by oxidation in the absence of CuO/La₂O₃ composite catalyst, and around 93.0% NH₃ reduction was achieved during catalytic oxidation over the CuO/La₂O₃ (8:2, molar/molar) catalyst at 400 °C with an oxygen content of 4.0%. Moreover, the effect of the reaction temperature on the removal of NH₃ in the gaseous phase was also monitored at a gas hourly space velocity of under 92,000 h^− 1.     

Monodispersed gold nanoparticles supported on γ-Al2O3 for enhancement of low-temperature catalytic oxidation of CO

Monodispersed nano-Au/γ-Al₂O₃ catalysts for low-temperature oxidation of CO have been prepared via a modified colloidal deposition route, which involves the deposition of dodecanethiolate self-assembled monolayer (SAM)-protected gold nanoparticles (C₁₂ nano-Au) in hexane on γ-Al₂O₃ at room temperature. The diameter of the gold nanoparticles deposited on the support is 2.5 ± 0.8 nm after thermal treatment, and their valence states comprise both the metallic and oxidized states. It is found that the thermal treatment temperature affects significantly the catalytic activity of the catalysts in the processing steps. The catalyst treated at 190 °C exhibits considerably higher activity as compared to catalysts treated at 165 and 250 °C. A 2.0-wt.% nano-Au/γ-Al₂O₃ catalyst treated at 190 °C for 15 h maintains the catalytic activity at nearly 100% CO oxidation for at least 800 h at 15 °C, at least 600 h at 0 °C, and even longer than 450 h at −5 °C. Evidently, the catalysts obtained using this preparation route show high catalytic activity, particularly at low temperatures, and a good long-term stability.     

Electrochemical effect of gold nanoparticles on Pt/α-Fe2O3/C for use in methanol oxidation in alkaline solution

A catalyst containing gold nanoparticles with Pt/α-Fe₂O₃/C was prepared by a co-precipitation method and its catalytic activity for the oxidation of methanol, formaldehyde, and formic acid in alkaline solutions was evaluated by an electrochemical method and high-performance liquid chromatography (HPLC). The addition of gold nanoparticles improved catalytic activity only for the oxidation of methanol and formaldehyde, and not for the oxidation of formic acid. HPLC analysis was performed for methanol oxidation to detect the oxidative products. In HPLC analysis, only formate anion could be detected in the electrolyte solution and the ratio of formate anion obtained to the total passed charge in Pt/nano-Au/α-Fe₂O₃/C was less than that in Pt/C, indicating that formic acid is not the final product of methanol oxidation. These results show that gold nanoparticles promoted methanol oxidation up to CO₂.     

Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

CO adsorption over Pd₄ and Pt₄ cluster supported by c-ZrO₂(1 1 1) and CeO₂(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt₄/c-ZrO₂ and Pt₄/CeO₂ show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt₄ cluster. c-ZrO₂ supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO₂ supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M₄ clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer.     

介孔CuCe/M/CuCe(M=Co,Mn,Zr)催化剂富H_2中优先氧化CO的催化性能

优先氧化是去除富H2中CO最有效的方法,铜铈催化剂是该领域的研究热点。以SBA-15为模板剂,采用纳米刻蚀法合成系列介孔Cu Ce/M/Cu Ce(M=Co,Mn,Zr)催化剂,采用XRD、N2吸附-脱附、TEM、H2-TPR和O2-TPD对催化剂结构及形貌进行表征,并对其在富H2中CO优先氧化性能进行研究。结果表明,Mn有利于催化剂表面吸附氧的增加,有助于大量氧空位的产生,进而促进CO优先氧化性能的提高;Zr的加入抑制了Cu O的还原,且其表面氧脱附温度范围过宽,不利于催化剂催化氧化性能的释放。掺杂Co与Mn可以形成Ce-Cu-M-O固溶体,促进了催化剂表面氧和晶格氧之间的相互转化,最终有利于铜铈催化剂CO优先氧化性能的提高。     

M-MOF-74(M=Ni,Co,Zn)的制备及其电化学催化合成氨性能

将自然界丰富的氮转化为氨对人类社会发展至关重要。以氮和水为原料的电化学合成氨是极具应用前景的绿色合成过程。采用水热法合成了Ni-, Co-和Zn-MOF-74催化剂,采用XRD、SEM以及XPS等表征了催化剂结构,并在0.1 mol·L-1Na2SO4电解液中研究了它们的电催化合成氨性能。结果表明,在常温常压下,Ni-MOF-74的电催化合成氨性能优于Co-和Zn-MOF-74催化剂,在-0.7 V (vs Ag/Ag Cl)下其氨合成速率和法拉第效率分别高达6.68×10-11mol·s-1·cm-2和23.69%,这归因于Ni-MOF-74不仅颗粒尺寸小且分布均匀,而且具有最多的金属-氧键和最大的电化学比表面。特别是Ni-MOF-74还能有效抑制析氢副反应,从而提高了法拉第效率。     

Adsorption of N2 and CO2 on Activated Carbon,AlO(OH) Nanoparticles,and AlO(OH) Hollow Spheres

Adsorption behaviors of nitrogen and CO₂ on Norit R1 Extra and AlO(OH) nanoparticles and hollow spheres were measured under different temperature and pressure conditions using a magnetic suspension balance. Independent from the substrate investigated, all isotherms increase at lower pressure, reach a maximum, and then decrease with increasing pressure. In addition, selected experimental data were correlated with different model approaches and compared with reliable literature data. In case of CO₂ on AlO(OH), capillary condensation was observed at two defined temperatures. The results suggest that the conversion of the liquid into a supercritical adsorbate phase does not take place suddenly.     

Ecotoxicology of carbon-based engineered nanoparticles: Effects of fullerene (C60) on aquatic organisms

To more fully assess the toxicity of water-soluble fullerene (nC₆₀), acute toxicity assays were performed on several environmentally relevant species. Included were the freshwater crustaceans Daphnia magna and Hyalella azteca, and a marine harpacticoid copepod, and two fish species, fathead minnow Pimephales promelas and Japanese medaka Oryzias latipes. The latter two species were used to assess sublethal effects of fullerene exposure by also assessing mRNA and protein expression in liver. Because prior studies found that both sonication and using tetrahydrofuran to solubilize fullerene increased the toxicity of nC₆₀, the nC₆₀ used in this study was prepared by stirring. For the invertebrate studies, nC₆₀ could not be prepared at high enough concentration levels to cause 50% mortality (LC₅₀) at 48 or 96 h. The maximum concentrations tested were 35 ppm for freshwater and 22.5 ppm for full-strength (35 ppt) seawater, since at higher concentrations the nC₆₀ precipitated out of solution. Daphnia 21-day exposures resulted in a significant delay in molting and significantly reduced offspring production at 2.5 and 5 ppm nC₆₀, which could possibly produce impacts at the population-level. For the fish, we found that neither the mRNA nor protein-expression levels of cytochrome P450 isozymes CYP1A, CYP2K1 and CYP2M1 were changed. The peroxisomal lipid transport protein PMP70 was significantly reduced in fathead minnow, but not medaka, indicating potential changes in acyl-CoA pathways.     

Self-assembled fabrication of a polycrystalline boron-doped diamond surface supporting Pt (or Pd)/Au-shell/core nanoparticles on the (111) facets and Au nanoparticles on the (100) facets

Modified boron-doped diamond (BDD) surfaces supporting different, carefully selected types of metal nanoparticles on different types of crystal facets were fabricated via a self-assembly method. A hydrogen plasma-treated BDD surface was treated with UV/ozone for 10 s followed by immersion in a Au nanoparticle (AuNP) solution to fabricate a BDD surface selectively and densely supporting AuNPs on the (111) facet (AuNP₁₁₁-BDD). The AuNP₁₁₁-BDD sample was then immersed in H₂PtCl₆/ascorbic acid or H₂PdCl₄/sodium citrate to cover the AuNP surface with Pt or Pd (Pt/AuNP₁₁₁-BDD or Pd/AuNP₁₁₁-BDD). These samples were treated with UV/ozone for 40 s followed by re-immersion in the AuNP solution to immobilize AuNPs on the (100) facets (Pt/AuNP₁₁₁-AuNP₁₀₀-BDD or Pd/AuNP₁₁₁-AuNP₁₀₀-BDD). The metal nanoparticles supported on the BDD surface were confirmed by cyclic voltammetry to be electrochemically active. The crystal-facet-selective support of the metal nanoparticles was also confirmed by two-dimensional elemental mapping via field emission Auger electron spectroscopy. The macro procedures used for the crystal-facet-selective immobilization of the AuNPs was reproducible, and this technique should be applicable to the creation of a new class of advanced materials in such fields as optics, electronics, sensing, and (electro)catalysis.     

Endohedral metallofullerenes M@C82 (M=La, Y): synthesis and transport properties

Endohedral metallofullerenes M@C_2n (M=La, Y) were synthesized by the arc-discharge method using optimum electric arc parameters. It was also shown that an organic solvent (N,N-dimethylformamide) is successfully used in selective extraction of M@C_2n. We identified the resulting products by mass spectrometry, electron spectrophotometry, EPR and X-ray fluorescence spectroscopy. The resulting N,N-dimethylformamide extracts of La@C_2n and Y@C_2n are shown to be free of empty fullerenes and appear as a mixture of endometallofullerenes M@C_2n whose main ingredient is M@C₈₂ (∼80 wt%). Transport properties of the extracts of La@C₈₂ and Y@C₈₂ were studied using pressed pellets. It was found that oxygen and heat treatment affect conductivity of endometallofullerenes. Heat treatment results in a three-order increase of conductivity from 10⁻⁵ upto 10⁻² Ohm⁻¹ cm⁻¹