A comparative study for the electrocatalytic oxidation of alcohol on Pt-Au nanoparticle-supported copolymer-grafted graphene oxide composite for fuel cell application

The platinum-gold bimetallic nanoparticles supported poly(cyclotriphosphazene-co-benzidine)-grafted graphene oxide (poly(CP-co-BZ)-g-GO) composite has been prepared for electrochemical performance studies. Cyclic voltammetry and chronoamperometric studies were carried out to check the electrochemical properties of Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO catalysts for methanol, ethylene glycol and glycerol in alkaline medium. The morphology and crystalline structure of the prepared Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO and catalysts have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). From the electrochemical results, it was concluded that Pt-Au/poly(CP-co-BZ)-g-GO catalyst shows higher catalytic activity and stability compared to Pt/poly(CP-co-BZ)-g-GO catalyst. The catalytic activity of Pt/poly(CP-co-BZ)-g-GO catalyst has been compared with Pt/poly(CP-co-BZ), Pt/GO and Pt/C catalysts. In addition, oxidation current of ethylene glycol is higher than the methanol and glycerol in alkaline medium on the prepared catalyst.     

Preparation and characteristic of platinum catalyst deposited on boron-doped carbon nanotubes

In this work, boron doped multi-walled carbon nanotubes (BMWNTs) were introduced as a Pt catalyst support due to their unique physicochemical properties. The effect of BMWNTs on methanol oxidation was investigated with different Pt loading contents. The surface and structural properties of the modified MWNT supports were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), respectively. The Pt loading contents in the catalysts were confirmed by inductive coupled plasma-mass spectrometer (ICP-MS) and the morphological structures of the catalysts were analyzed by transmission electron microscopy (TEM). The electrocatalytic activity of Pt/MWNTs was investigated by cyclic voltammetry measurement. As a result, the boron oxide vapor reacted with MWNTS to form BMWNTs, which led to enhancing the properties, such as graphitization and electrochemical behaviors. Moreover, Pt deposited on BMWNTs exhibited better electrocatalytic activity than on MWNTs for methanol oxidation. Consequently, it was found that partial boron doped MWNTs could influence on the properties of the MWNTs, resulting in enhancing the electrocatalytic activity of the catalysts for DMFCs.     

Synthesis and characterization of Pt–Sn–Ce/MC ternary catalysts for ethanol oxidation in membraneless fuel cells

The present work represents the mesoporous carbon-supported Pt–Sn and Pt–Sn–Ce catalysts with different mass ratios have been prepared by co-impregnation reduction method. The prepared catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM) investigation. The XRD patterns of prepared Pt/MC (100) Pt–Sn/MC (75:25), Pt–Ce/MC (75:25), and Pt–Sn–Ce/MC (75:20:05) catalysts showed that Pt metal was the predominant material in all the samples, with peaks attributed to the face-centered cubic (fcc) crystalline structures. Additionally changes in the lattice parameters observed for Pt suggest the incorporation of Sn into the Pt crystalling structure with the formation of an alloy mixture with the SnO₂ phase. The TEM analysis designates that the prepared catalysts had similar particle morphology, and their particle sizes were 2–5 nm. The electrochemical studies showed that ternary catalyst shows best performance for oxidation of ethanol molecule at normal temperature. The enhanced ethanol oxidation activity for the ternary Pt–Sn–Ce catalyst is mainly attributed to the synergistic effect of bifunctional mechanism with electronic effect. Additionally, chemical nature of ceria affords oxygen-containing molecule to oxidize acetaldehyde to acetic acid. In this present context, 1 M ethanol was used as a fuel, 0.1 M sodium perborate was used as an oxidant, and 0.5 M sulfuric acid was used as an electrolyte. In mesoporous carbon-supported binary Pt–Sn and ternary Pt–Sn–Ce anode catalysts were effectively tested in a single membraneless fuel cell at normal temperature. The presence of Sn and Ce enhances the CO oxidation; they produced an oxygen-containing species to oxidize acetaldehyde to acetic acid.     

Electrocatalytic performance of bimetallic platinum–ruthenium nanoclusters supported on graphite nanofibers

In this work, graphite nanofibers (GNFs) as a catalysts supports were impregnated with Pt and Ru precursor compounds to investigate the effect of various Pt–Ru compositions on the catalytic activity of direct methanol fuel cells (DMFCs). The particle sizes and morphological structures of the catalysts were analyzed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The electrochemical oxidation of the prepared catalysts was investigated by cyclic voltammetry (CV) measurement. Inductive coupled plasma-mass spectrometer (ICP-MS) analysis showed that the metallic ratio in the catalysts was very near to expectations. Cyclic voltammetry showed that the catalysts were electro catalytically active in the methanol oxidation. Among the prepared catalysts, the Pt₅₀Ru₅₀ catalysts exhibited the best electrocatalytic performance. It was concluded that catalytic activity is dependent on the alloy compositions of the catalysts, and that Ru metal has a positive effect on CO poisoning of Pt metal for methanol oxidation.     

Preparation of highly dispersed Pt-SnOx nanoparticles supported on multi-walled carbon nanotubes for methanol oxidation

To maximize the utilization of catalysts and thereby reduce the high price, a new strategy was developed to prepare highly dispersed Pt-SnO_x nanoparticles supported on 8-Hydroxyquinoline (HQ) functionalized multi-walled carbon nanotubes (MWCNTs). HQ functionalized MWCNTs (HQ-MWCNTs) provide an ideal support for improving the utilization of platinum-based catalysts, and the introduction of SnO_x to the catalyst prevents the CO poisoning effectively. The as-prepared catalysts are characterized by Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It is found that the HQ functionalization process preserves the integrity and electronic structure of MWCNTs, and the resulting Pt-SnO_x particles are well dispersed on the HQ-MWCNTs with an average diameter of ca. 2.2 nm. Based on the electrochemical properties characterized by cyclic voltammetry and chronoamperometry, the Pt-SnO_x/HQ-MWCNTs catalyst displays better electrocatalytic activity and stability for the methanol oxidation. It is worth mentioning that the forward peak current density of Pt-SnO_x/HQ-MWCNTs catalyst is ca. 1.9 times of that of JM commercial 20% Pt/C catalyst, which makes it the preferable catalyst for direct methanol fuel cells.     

Novel synthesis and characterization of nanocomposite Pt-WO3-TiO2/C electrocatalyst for PEMFC

In this study, an effective preparation of Pt-WO₃-TiO₂/C electrocatalysts has been developed for polymer electrolyte membrane fuel cell (PEMFC) application. The single cell performance of Vulcan XC-72R carbon-supported Pt-WO₃-TiO₂ electrocatalysts with various compositions (as weight percentage Pt-W-Ti 0:5:5, 2:4:4, 4:3:3, 6:2:2, and 8:1:1) as anode materials are investigated in PEMFC. These catalysts are compared with 10 % Pt/C on the same Vulcan XC-72R carbon support and 10 % Pt/C (commercial) electrocatalyst. The physical and morphological characterization of the optimized Pt-WO₃-TiO₂/C, 10 % Pt/C, and 10 % Pt/C (commercial) electrocatalysts are further investigated by X-ray diffraction (XRD), cyclic voltammetry, scanning electron microscopy with energy-dispersive X-ray analysis, and transmission electron microscopy (TEM) techniques. Among all the molar ratio of the catalysts, the Pt-W-Ti (4:3:3) molar ratio catalyst exhibited the larger electrochemical active surface area. The electrochemical performance of Pt-WO₃-TiO₂/C (with a weight percentage of Pt-W-Ti 4:3:3) as anode material is better than those of other compositions of Pt-WO₃-TiO₂/C catalysts. The amount of platinum was also reduced from 1.76 to 0.704 mg cm^?2 which exhibited higher performance in single cell tests. Platinum shows a smaller-sized crystalline structure in XRD and TEM analysis. High performance indicates that enhanced proton transport occurs through the use of this catalyst.     

Pt/TiO2催化剂的载体结构对甲醇催化氧化性能的影响

二氧化钛载体包括二氧化钛纳米管阵列(TNTAs)和二氧化钛纳米线阵列(TNWAs)两种,载体的结构不同对催化性能有一定的影响。然而,Pt负载在TNTAs和TNWAs催化性能的比较鲜有报道。本文通过微波法制备了Pt/TNTAs和Pt/TNWAs两种催化剂,结果表明,Pt/TNTAs催化甲醇氧化效果要优于Pt/TNWAs。相较于Pt/TNWAs, Pt/TNTAs的优越催化性能可能与纳米管的限域效应有关。可见,载体的结构对催化剂的性能有很大的影响。     

Silica nanoparticles surface-modified with thiacalixarenes selectively adsorb oligonucleotides and proteins

In this study, platinum nanoparticles have been prepared using PtCl₄ as a starting material and 1-hexylamine, N-methylhexylamine, N,N-dimethylhexylamine, 1-heptylamine, N-methylheptylamine, and N,N-dimethylheptylamine as surfactants. All these surfactants were used in this synthesis, for the first time, to explore the effect of primary, secondary, and tertiary amine and chain length on the size and catalytic activity toward C1–C3 alcohol electro-oxidation. The electrochemical performance of all catalysts was determined using cyclic voltammetry and chronoamperometry. These techniques indicate that the highest electrocatalytic performance was generally observed when electrochemical surface area (ECSA), percent platinum utility, roughness factor, and the number of CH₃ groups attached to the nitrogen atom is higher and the chain length shorter (C₆H₁₃). In addition, other important properties such as the crystal structure of platinum, size, and distribution of the platinum nanoparticles on the carbon support, and Pt(0) to Pt(IV) ratio, were determined using X-ray photoelectron spectroscopy, X-ray diffraction, atomic force microscopy, and transmission electron microscopy. It was found that increasing ECSA, Pt(0)/Pt(IV) ratio, % Pt utility, and roughness factor improves the C1–C3 alcohol oxidation catalytic performance.     

Nitrogen‐Doped Carbon with Mesopore Confinement Efficiently Enhances the Tolerance,Sensitivity, and Stability of a Pt Catalyst for the Oxygen Reduction Reaction

Electrocatalysts for the oxygen reduction reaction (ORR) present some of the most challenging vulnerability issues reducing ORR performance and shortening their practical lifetime. Fuel crossover resistance, selective activity, and catalytic stability of ORR catalysts are still to be addressed. Here, a facile and in situ template‐free synthesis of Pt‐containing mesoporous nitrogen‐doped carbon composites (Pt‐m‐N‐C) is designed and specifically developed to overcome its drawback as an electrocatalyst for ORR, while its high activity is sustained. The as‐prepared Pt‐m‐N‐C catalyst exhibits high electrocatalytic activity, dominant four‐electron oxygen reduction pathway, superior stability, fuel crossover resistance, and selective activity to a commercial Pt/C catalyst in 0.1 m KOH aqueous solution. Such excellent performance benefits from in situ covalent incorporation of Pt nanoparticles with optimal size into N‐doped carbon support, dense active catalytic sites on surface, excellent electrical contacts between the catalytic sites and the electron‐conducting host, and a favorable mesoporous structure for the stabilization of the Pt nanoparticles by pore confinement and diffusion of oxygen molecules.     

Successive electrodeposition of polydopamine and PtPd metal on a graphene oxide support for use as anode fuel cell catalysts

Successive electropolymerization of dopamine and electrodeposition of Pd and/or Pt on a graphene oxide (GO) support were used to prepare anode catalysts for low-temperature fuel cells. Transmission electron microscopy images were used to investigate the morphologies and distribution of the prepared catalysts, which showed the metal formed as nanoparticles on the catalysts. The GO surface was favorable for the modification with electropolymerized polydopamine (PDA) and the electrodeposition of metal catalyst nanoparticles using a simple preparation process. The PDA-loaded GO composite was used as a matrix for the dispersion of Pt and Pd nanoparticles. GO could be simultaneously modified by PDA and reduced without using reducing agents. The electrocatalytic performance of the catalysts for the oxidation of selected small molecule fuels (e.g., methanol, ethanol and formic acid) was examined. An outstanding catalytic activity and stability was found for the prepared Pt/Pd/PDA/GO composite, which was attributed to the high active surface area.     

Electrochemical codeposition of Pt/graphene catalyst for improved methanol oxidation

Pt/graphene electrocatalyst was uniformly deposited on a glassy carbon substrate using a pulsed galvanostatic electrodeposition method, which facilitated the simultaneous electrochemical reduction of graphene oxide and formation of Pt nanoparticles. Compared to the commercial carbon-supported Pt electrocatalyst, the electrochemically reduced Pt/graphene (Pt/ERG) catalyst exhibited improved electrocatalytic activity for methanol oxidation due to the synergistic effects of an increase in the number of catalytic reaction sites and an enhancement of the charge transfer rate.     

Ordered intermediate compound PtBi-modified Pt/C catalyst for 2-propanol electrooxidation in alkaline medium

The PtBi-modified Pt/C catalyst was prepared by liquid chemical reduction method. X-ray diffraction and X-ray photoelectron spectroscopy (XPS) were used to characterize PtBi-modified Pt/C catalyst. The electrochemical behaviors for the 2-propanol electrooxidation reaction in alkaline medium were measured by cyclic voltammetry, line sweep voltammetry, and electrochemical impedance spectra (EIS). The results showed that the prepared PtBi is ordered intermediate compound. Compared with the spectrum obtained from Pt/C catalyst, the XPS peak of PtBi-modified Pt/C catalyst is obviously moving toward the low Pt 4f biding energy. The Bi⁰ and Bi₂O₃ coexist on the surface of PtBi/C catalyst. In alkaline medium, the electrochemical activity of 2-propanol electrooxidation of PtBi/C catalyst is higher than that of commercial Pt/C catalyst. EIS result shows that the reaction mechanism of 2-propanol electrooxidation for both catalysts is similar.     

Direct methanol fuel cells: The influence of methanol on the reduction of oxygen over Pt/C catalysts with different particle sizes

Two Pt/C catalysts with different particle sizes (Pt/C: 2.5 nm, Pt/C-700Ar: 5.1 nm) were investigated by applying a half-cell configuration —rotating disk electrode (RDE) technique in H₂SO₄ aqueous solutions in the absence of or in the presence of methanol with different concentrations. Pt/C catalyst exhibited higher mass activity in H₂SO₄ aqueous solution without methanol and slightly lower mass activity in H₂SO₄ plus 0.1 mol/L CH₃OH in comparison with that of Pt/C-700Ar catalyst. On the contrary,single direct methanol fuel cell (DMFC) tests showed that Pt/C exhibited higheroxygen reduction reaction (ORR) activity and better cell performance, mainly due to the different kinds of electrolyte properties. Furthermore, it suggested that a better single DMFC performance could be obtained with a smaller particle size Pt-based cathode catalyst. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 — 18, 2004.     

B,N-codoped 3D micro-/mesoporous carbon nanofibers web as efficient metal-free catalysts for oxygen reduction

B, N-codoped carbon nanofibers were massively prepared by heat treatment of electrospun carbon nanofibers with the mixture of boric acid/urea in N₂ (BNC_f-N) and subsequently activated in NH₃ (BNC_f-NA). The directly electrospun self-standing 3D non woven structure with void spaces between each fiber facilitates the mass transport of reactant and resulted molecules. Further NH₃ activation gives BNC_f-NA a high surface area of 306.3 m² g⁻¹ with micro/mesoporous structure, providing abundant passageway for proton transfer. Simultaneously, NH₃ activation also realizes the optimization of surface functionalities, such as more B–N–C and pyridinic-N. These intriguing features render BNC_f-NA excellent catalytic behavior with nearly four-electron oxygen reduction reaction (ORR) process in alkaline media, especially much better stability and methanol tolerance than the commercial Pt/C catalyst. Our work provides a large-scale preparation method for efficient metal-free catalysts toward ORR, thus further intensifying the commercial application of fuel cells.     

Kinetic investigations and product analysis for optimizing platinum loading in direct ethanol fuel cell (DEFC) electrodes

In this investigation, attempt has been taken to optimize Pt loading in chemically synthesized carbon-supported Pt catalyst for ethanol electro-oxidation. Surface morphology and structural characteristics showed that the catalyst matrix of 40% Pt/C is formed with homogeneously distributed and reduced particle size compared with the other catalysts. The electrochemical techniques were employed to investigate on the kinetics and mechanism of ethanol electro-oxidation at room temperature. The reaction intermediates formed during the electro-oxidation of ethanol was estimated by ion chromatography and the highest yield of acetate on 40% Pt/C substantiates the catalytic superiority of this electrode over the others. Finally, the catalytic performance of this electrode was compared with an electrodeposited electrode with much higher content of Pt, and it was summarized that the chemical method of deposition is much more effective than electroplating exhibiting high electrocatalytic activity towards ethanol oxidation.     

A novel humidity sensor based on NH2-MIL-125(Ti) metal organic framework with high responsiveness

Noble metal nanostructures with branched morphologies [i.e., 3-D Pt nanoflowers (NFs)] by tri-dimensionally integrating onto conductive carbon materials are proved to be an efficient and durable electrocatalysts for methanol oxidation. The well-supported 3-D Pt NFs are readily achieved by an efficient cobalt-induced/carbon-mediated galvanic reaction approach. Due to the favorable nanostructures (3-D Pt configuration allowing a facile mass transfer) and supporting effects (including framework stabilization, spatially separate feature, and improved charge transport effects), these 3-D Pt NFs manifest much higher electrocatalytic activity and stability toward methanol oxidation than that of the commercial Pt/C and Pt-based electrocatalysts.     

Hydrothermal synthesis and high electrochemical performance of ordered mesoporous Co/CMK-3 nanocomposites

A novel ordered mesoporous Co/CMK-3 nanocomposites were successfully fabricated via a facile hydrothermal method. XRD patterns affirmed that the CoCl₂ entirely reduced to metal Co. Cobalt particles were well-dispersed and embedded in the mesochannels of the CMK-3 according to the nitrogen adsorption-desorption technique and transmission electron microscopy (TEM) images. Electrochemical test shows that cobalt nanoparticle can significantly promote the electrochemical properties of CMK-3 leading to a remarkable enhancement of the reversible capacity, cyclic stability, and rate capacity. The Co/CMK-3 nanocomposites were delivering a high reversible capacity of 674 mAh g^?1 at the current density of 50 mA g^?1 after 50 cycles, which was much higher than that of original CMK-3 (400 mAh g^?1). The Co/CMK-3 nanocomposites also demonstrate an excellent rate capability. The improved lithium storage properties of ordered Co/CMK-3 nanocomposites can be attributed to the CMK-3 that could restrain the aggregation of Co nanoparticles, the large surface area of the mesopores in which the Co nanoparticles are formed, as well as presence of Co which played the role of catalyst could promote the lithium storage reaction.     

Preparation of nano-sized platinum metal catalyst using photo-assisted deposition method on mesoporous silica including single-site photocatalyst

Pt particles in a uniform dispersion were successfully synthesized on single-site photocatalyst (Ti-containing mesoporous silica (Ti-HMS)) under UV-light irradiation by a photo-assisted deposition (PAD) method. Using an aqueous solution of H₂PtCl₆ as a precursor, the nano-sized Pt metal particles were deposited directly on the photo-excited tetrahedrally coordinated titanium oxide moieties within the framework of mesoporous silica (PAD-Pt/Ti-HMS). The Pt catalysts were characterized by means of XRD, Pt L_III-edge XAFS, CO adsorption, and TEM analysis. It was demonstrated that Pt particles had mean diameter of 4 nm in a narrow size distribution. Meanwhile, Pt particles loaded by a conventional impregnation method (imp-Pt/Ti-HMS) showed a wide size distribution ranging from 2 to 30 nm. The PAD-Pt/Ti-HMS catalyst was more active in the CO oxidation than the conventional impregnated imp-Pt/Ti-HMS catalyst. It is suggested that the PAD method using single-site photocatalyst is a useful and unique technique to prepare fine and uniform Pt nanoparticles.     

PtCu二元金属催化剂抗CO中毒性能的理论研究

基于密度泛函第一性原理研究了M-graphene(M=Pt,Cu,PtCu;graphene:pristine,Stonewales,Single-vacancy graphene)催化剂的抗CO中毒能力.对于纯Pt和纯Cu吸附在石墨烯上时,Pt的吸附能力最强,吸附结构最稳定.当Pt中掺杂Cu后,PtCu二元金属催化剂在石墨烯上的吸附结构的稳定性进一步增强.通过对M-graphene-CO吸附结构的研究,发现以缺陷石墨烯为载体的金属催化剂的抗CO中毒能力优于以原始石墨烯为载体的同种金属催化剂,PtCu二元金属催化剂抗CO中毒能力明显好于纯Pt和纯Cu的抗毒性.因此,缺陷石墨烯载体以及掺杂Cu的PtCu二元金属催化剂,对于提高催化剂的稳定性和抗CO中毒能力起到了重要的作用.     

Differences in catalytic properties between mesoporous and nanoparticulate platinum

Conventional Pt/Al₂O₃ catalysts prepared by wet-impregnation are composed of Pt nanoparticles exposing convex and facetted surfaces deposited on high-surface area γ-Al₂O₃ supports. A hexagonal phase mesoporous Pt material (denoted H₁-Pt) prepared by chemical reduction in the aqueous domains of a lyotropic liquid crystalline template exposes however mainly a concave surface with expected different catalytic properties. A series of Pt/Al₂O₃ catalysts were prepared using H₁-Pt, Pt-black or wet-impregnated Pt, and the samples were characterized by SEM-EDX and TEM, and finally evaluated for CO oxidation. The H₁-Pt/Al₂O₃ catalyst showed an ignition profile for CO oxidation at lower temperatures and thus appeared less sensitive to CO poisoning than the two other types of samples. This difference may be related to the differences in surface curvature.