Improved electrocatalytic kinetics of nickel hydroxide nanoparticles on Vulcan XC-72R carbon black towards alkaline urea oxidation reaction

Nickel hydroxide nanoparticles were fabricated on Vulcan XC-72R carbon black using various reducing agents through assisted microwave polyol process. The formed electrocatalysts using sodium borohydride [Ni(OH)₂/C–NB], ethylene glycol [Ni(OH)₂/C–EG] and a mixture of them [Ni(OH)₂/C–EGNB] displayed an electrocatalytic activity towards urea oxidation in NaOH solution. The oxidation peak potential and current density values were greatly influenced by the employed reducing agent. Lower onset and peak potential values were measured at Ni(OH)₂/C–EGNB, while Ni(OH)₂/C–EG exhibited the highest oxidation current density during urea oxidation reaction. Electroactive surface area measurements revealed that the number of available active sites for the oxidation reaction was arranged in an ascending order as Ni(OH)₂/C–NB < Ni(OH)₂/C–EGNB < Ni(OH)₂/C–EG. The diffusion coefficient of urea molecules at Ni(OH)₂/C–EG and Ni(OH)₂/C–EGNB was 14.69 and 5.90 times higher than that at Ni(OH)₂/C–NB. Stable performance was measured at all studied electrocatalysts over prolonged operation suggesting their valuable application as efficient anode materials in direct urea oxidation fuel cells.     

Fundamentals of hydrogen storage processes over Ru/SiO2 and Ru/Vulcan

Hydrogen adsorption and desorption over Ru/SiO₂ and Ru/Vulcan are investigated in terms of hydrogen storage and release characteristics by both dynamic and static experiments. Ru particle dispersions as a function of metal loading were determined by HR-TEM and volumetric chemisorption experiments. Vulcan was more accommodating for spillover hydrogen than SiO₂. High Ru dispersions, i.e., small particle sizes, favored the amount of hydrogen spillover to Vulcan, as revealed by temperature programmed desorption (TPD) of hydrogen. TPD of hydrogen under He flow experiments over Ru/SiO₂ and Ru/Vulcan materials revealed a low temperature process (up to 200 °C) attributed to desorption of weakly bound hydrogen from Ru metal surface. A high temperature process (above 450 °C) was attributed to diffusion of hydrogen from the support to the Ru particle and desorption at the Ru sites. Hydrogen adsorbs strongly on Ru metal, as indicated by the initial heats of H₂ adsorption measured as 100 kJ/mol over 1 wt% Ru/Vulcan by adsorption calorimetry. At higher coverages, heat of adsorption of hydrogen was measured as 10 kJ/mol. Low heat of adsorption of hydrogen at high coverages indicate multilayer weak adsorption of hydrogen over the storage material, which can desorb at lower temperatures.     

Key parameters of active layers affecting proton exchange membrane (PEM) fuel cell performance

The 2ⁿ full factorial design was applied to identify the key parameters of the active layer affecting the performance of a proton exchange membrane (PEM) fuel cell. Three main selected parameters were considered: carbon-type (Vulcan XC 72R and Black Pearls 2000 conducting furnace blacks, Cabot Corporation Boston, MA), Pt loading (0.1 and 0.5 mg/cm²), and Nafion™ sulfonic acid fluoropolymer (Du Pont de Nemours, Wilmington, DE) ionomer content (10% and 60%) for variables A, B, and C, respectively. The results from full factorial analysis indicated that the key factors affecting the exchange current density or activation loss were Pt loading whereas the key factors controlling the resistance due to ohmic loss were Nafion content and carbon type. In addition, there are the interactions between these parameters controlling the thin-film active layer performance, especially the interaction of carbon type and Nafion content. From cyclic voltammograms and cell performance testing, a Nafion content of 30% in a catalyst layer consisting of 0.5 mg/cm² Pt on Vulcan XC 72R is optimal.     

Thermally Pretreated 46% Pt/Vulcan XC72: Characterisation by TGA/DSC/TEM and Cyclic Voltammetry

We report a study of thermal stability and impact of thermal pretreatment procedures for 46% Pt/Vulcan XC72 (Tanaka) fuel cell catalyst. Stability in air and in inert gas (nitrogen, argon, helium) has been investigated by thermal gravimetric analysis (TGA), TGA‐mass spectrometry (TGA‐MS) and differential scanning calorimetry (DSC). Two distinct low temperature mass loss processes (100–200 and 285–300 °C) were observed, each exhibiting unique pretreatment temperature dependencies. TGA‐MS data in helium show fragment ions that suggest the thermal degradation processes are associated with decomposition of materials such as processing aids. Transmission electron microscopy (TEM) reveals a modest increase in average Pt nanoparticle size upon thermal pretreatment. After a pretreatment protocol based on TEM and thermal characterisation (300 °C/15 min, N₂), the electrochemically active surface area did not increase. At the kinetically controlled potential region (E >0.8 V) there was a small drop in current density for treated 46% Pt/C in comparison with as‐received catalyst. The slowing in ORR kinetics is significant. Apparently, the removal of organic components, which would improve mass transport, is negated by increased nanoparticle size.     

The Influence of Pt Loading,Support and Nafion Content on the Performance of Direct Methanol Fuel Cells: Examined on the Example of the Cathode

Nano‐sized Pt colloids were prepared using the polyol method and supported on Ketjen black EC 600J (KB), Vulcan XC‐72 (VC) and high surface area graphite 300 (HG). The effects of the Nafion ionomer content, and the Pt loading of the cathode catalyst layer as well as the Pt loading on the support on the performance of direct methanol fuel cells (DMFCs), were studied. The membrane electrode assemblies (MEAs) were analysed using current–voltage curves, cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and adsorbed CO stripping voltammetry. Optimum Nafion to carbon (N/C) ratios (N/C being defined as the weight ratio of the Nafion ionomer to the carbon) were determined. The optimum N/C ratios were found to depend on the support as follows, 1.4, 0.7 and 0.5 for Pt/KB, Pt/VC and Pt/HG, respectively and to be independent of the Pt/C loading range of 20–80 wt% tested in this work. The highest DMFC performances, as well as the highest electrochemical active surface areas, and improved gas diffusivities, were achieved using these ratios. For the catalysts prepared in this work, the average Pt crystallite size was found to decrease with increasing surface area of the support for a particular Pt loading. MEAs made using KB as support and the optimal N/C ratio of 1.4 showed the best performances, i.e. higher than the VC and HG supports for any N/C ratio. The highest DMFC performance was observed using 60 wt% Pt on KB cathode electrodes of 1 mg Pt cm^–2 loading and an N/C value of 1.4. For all three supports studied, the 60 wt% Pt on carbon loading resulted in the best DMFC performance. This may be linked to the Pt particle size and catalyst preparation method used in this work. In comparison to literature results, high DMFC performances were achieved using relatively ‘low' Pt and Ru loadings. For example, a maximum power density of >100 mW cm^–2 at 60 °C was observed using a 1 mg Pt cm^–2 cathode loading and a 2 mg PtRu cm^–2 anode loading.     

Vulcan软件在三维地质建模中的应用——以胶东某金矿为例

Vulcan软件是功能强大的三维建模软件,在全球矿业企业中有广泛的应用。本文以胶东某金矿为例,介绍利用vulcan软件进行三维地质建模的方法步骤及使用效果。结果表明vulcan软件在三维地质建模的应用中是高效可行的。     

An effective electrocatalyst based on platinum nanoparticles supported with graphene nanoplatelets and carbon black hybrid for PEM fuel cells

A facile synthesis at room temperature and at solid-state directly on the support yielded small, homogeneous and well-dispersed Pt nanoparticles (NPs) on CB-carbon black, GNP-graphene nanoplatelets, and CB-GNP-50:50 hybrid support. Synthesized Pt/CB, Pt/GNP and Pt/CB:GNP NPs were used as electrocatalysts for polymer electrolyte membrane fuel cell (PEMFC) reactions. HRTEM results displayed very small, homogeneous and well-dispersed NPs with 1.7, 2.0 and 4.2 nm mean-diameters for the Pt/CB-GNP, Pt/GNP and Pt/CB electrocatalysts, respectively. Electrocatalysts were also characterized by RAMAN, XRD, BET and CV techniques. ECSA values indicated better activity for graphene-based supports with 19 m² g⁻¹_Pt for Pt/GNP and 55 m² g⁻¹_Pt for Pt/CB-GNP compared to 10 m² g⁻¹_Pt for Pt/CB. Oxygen reduction reaction (ORR) studies and fuel cell tests were in parallel with these results where highest maximum power density of 377 mW cm⁻² was achieved with Pt/CB-GNP hybrid electrocatalyst. Both fuel cell and ORR studies for Pt/CB-GNP indicated better dispersion of NPs on the support and efficient fuel cell performance that is believed to be due to the prevention of restacking of GNP by CB. To the best of our knowledge, Pt/GNP and Pt/CB-GNP electrocatalysts are the first in literature to be synthesized with the organometallic mild synthesis method using Pt(dba)₃ precursor for the PEMFC applications.     

Preparation and catalytic activity of CO-resistant catalyst core-shell Au@Pt/C for methanol oxidation

Au@Pt core-shell nanoparticles were successfully synthesized by a successive reduction method and then assembled on Vulcan XC-72 carbon surface.Furthermore,its composition,morphology,structure,and activity towards methanol oxidation were characterized by UV-vis spectrometry,transmission electron microscopy (TEM),high-resolution TEM (HRTEM),X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS),and cyclic voltammetry (CV).Results reveal that Au@Pt/C catalyst has better activity towards methanol oxidation than the pure platinum prepared under the same conditions.When the atomic ratio of Au to Pt in the prepared Au@Pt/C catalyst is 1∶2,this catalyst exhibits best electrocatalytic activity towards methanol oxidation in acidic media,and the peak current density on this catalyst is ～2.0times higher than that on Pt/C catalyst.The better catalytic activity of Au@Pt/C results from its better resistance to toxic CO than Pt/C because the CO oxidation on Au@Pt/C is 60 mV more negative than the case on Pt/C.     

Morphology and surface structure of nanocarbon allotropes: A comparative study

Different carbon allotropes, including vulcan carbon, multiwall carbon nanotubes, graphene, and nanodiamonds, were processed by chemical purification and treated in a mixture of H₂SO₄–HNO₃. The materials were characterized by infrared and Raman spectroscopy as well as by scanning and transmission electron microscopy. Oxidative differences are indicated by Raman through the G band (～1570 cm^?1), D band (～1340 cm^?1), and G’ band (～2684 cm^?1). The crystal size (L_a) and purity, relative to the amorphous carbonaceous material, were studied as well, along with the morphological changes induced by the treatments.     

Physical and electrochemical evaluation of commercial carbon black as electrocatalysts supports for DMFC applications

This work presents results with noble metal catalysts, Pt and PtRu supported on Black Pearl with a higher surface area in comparison with carbon black Vulcan XC-72R and Vulcan XC72. The nanoparticles were synthesized following the alcohol reduction method. Brunauer–Emmet–Teller (BET) surface area analysis, X-ray diffraction (XRD), energy dispersive analysis by X-rays (EDAX), and high resolution transmission electronic microscopy (TEM) experiments were carried out to characterize the materials obtained. Cyclic voltammograms (CV) of catalysts using the porous thin layer electrode technique were obtained for the catalysts surface evaluation and for methanol oxidation to check the electrocatalytic behavior of these nanocatalyst systems.