Microstructure and hydrogen production activity of Pt–TiO2 prepared by precipitation–photodeposition

A series of Pt–TiO₂ photocatalysts were prepared by a facile precipitation–photoreduction method under different pH conditions, using H₂PtCl₆ as platinum precursor. The microstructure and chemical state of Pt loaded on the surface of TiO₂ were analyzed by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). It was revealed that the size and distribution of Pt nanoparticles on TiO₂ surface is closely related to the initial pH of H₂PtCl₆ solution. The optimal pH value for forming highly dispersed Pt nanoparticles is 12. The photocatalytic activities of the prepared samples were investigated in terms of hydrogen production. The results indicated that the Pt–TiO₂ sample prepared by precipitation–photodeposition method shows much higher activity than that prepared by traditional photodeposition method.     

甲醇重整反应中Pt/γ-Al2O3催化剂纳米Pt粒径与催化性能关系研究

利用硝基甲烷还原法在室温条件下得到了纳米Pt粒径可控的担载Pt/γ-Al₂O₃催化剂, 并利用甲醇重整反应为反应探针考察了Pt粒径与催化反应性能之间的关系, 发现催化反应的性能与担载贵金属颗粒粒径之间存在明显的相关性. 通过透射电镜(TEM)、X射线衍射(XRD)、程序升温还原(TPR)等测试手段对催化剂进行表征, 发现钠米Pt的粒径大小不但影响甲醇重整反应的活性, 同时也影响反应的选择性, 即催化剂的催化性能与担载贵金属粒径之间存在明显的尺度效应.     

Spontaneous deposition of Pt‐nanoparticles on HOPG surfaces

Pt nanoparticles were spontaneously generated by immersion of a highly ordered pyrolytic graphite substrate in a 1 mM H₂PtCl₆ + 0.05 M H₂SO₄ plating solution using different immersion times, modifying both size and density of the deposits. Atomic force microscopy images show Pt particles distributed preferentially on surface defects of the electrode, increasing their size and density with deposition time. Scanning electronic microscopy/energy‐dispersive X‐ray spectroscopy images confirmed the formation of Pt deposits after 2 h immersion, forming irregular agglomerates with different sizes distributed over the surface. The open circuit potential studies showed potentials close to the corresponding PtCl₆^2?/Pt and PtCl₄^2?/Pt couples, which would indicate that some of these processes took place at the interface. The voltammetric response of the supported Pt nanoparticles showed an increase in current density towards the hydrogen evolution reaction being more pronounced for deposits formed after an immersion time of 2 h. In this case, the voltammetric behavior was similar to polycrystalline Pt. Copyright © 2015 John Wiley & Sons, Ltd.     

Pyrolysis of chloroplatinic acid to directly immobilize platinum nanoparticles onto multi-walled carbon nanotubes

Platinum nanoparticles supported on multi-walled carbon nanotubes (Pt/MWCNTs) were first prepared by simple pyrolysis of H₂PtCl₆ solution. The structure of Pt/MWCNTs was characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), and the results showed that the diameter of the obtained platinum nanoparticles immobilized on MWCNTs was below 50 nm, although the obtained platinum nanoparticles were not well uniformly dispersed on the surface of MWCNTs. The electrocatalytic performance of Pt/MWCNTs electrode for methanol oxidation reaction (MOR) was also investigated by linear sweep voltammetry (LSV), indicating that it was possible to employ the obtained platinum nanoparticles as anode material in fuel cell. Developing a novel and simple method to prepare platinum nanoparticles onto MWCNTs is the main contribution of this letter. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 8, pp. 1050–1053. The text was submitted the authors in English.     

XPS Studies of PtCl4 and H2PtCl6·6H20 doped polyacetylene

The PtCl₄ and H₂PtCl₆-6H₂O doped polyacetylene were studied by X-ray photoelection spectroscopy and transmission electron microscopy. We found that both Pt 4f and Cl 2p peaks could be resolved into two components both with a splitting of ca. 1.5 eV. The higher binding energy components of Pt 4f peak is attributed to Pt⁴⁺ and the lower binding energy one to Pt²⁺ species. From quantitative analysis of the results of decomposition of both Pt 4f and Cl 2p peaks it was found that an atomic ratio of chlorine to platinum for Pt²⁺ species is (Cl) / (Pt) = 2 and that for Pt⁴⁺ species is (Cl) / (Pt) = 6 for both PtCl₄ and H₂PtCl₆·6H₂O doped polyacetylene. The C 1s peaks could be decomposed into two components separated by ca. 1 eV. The intensity of the higher binding energy component increased with increasing dopant concentration. These indicate that the platinum salt doping proceeds through charge transfer from polyacetylene chain to platinum atom resulting in a partial reduction from Pt⁴⁺ to Pt²⁺ state. The existence of PtCl₂ cluster on the surface of the doped polyacetylene film was supported by transmission electron microscopy and electron diffraction observations. These results indicate that a random distribution of the dopant along the macromolecular chain, and the charge per carbon atom in the metallic region of doped polyacetylene has been estimated to be 0.2 |e|. From these results the mechanism of the PtCl₃ and H₂PtCl₆·6H₂O doping process in polyacetylene is clarified as follows: Thus the dopant anion in polyacetylene is PtCl,^2? for both PtCl₄ and H₂PtCl₆·6H₂O doping.     

纳米三氧化钨修饰碳纳米管载铂催化剂对甲醇氧化的电催化性能

采用表面修饰技术将碳纳米管(CNT)表面羧基化, 通过羧基将钨离子基团修饰到碳纳米管的外表面, 再通过高温焙烧处理将钨离子基团氧化成WO₃, 成功合成了纳米WO₃/CNT复合物, 进一步还原Pt 的前驱体而得到Pt-WO₃/CNT复合催化剂. 采用X射线粉末衍射(XRD)和透射电镜(TEM)对样品的形貌和晶型结构进行了表征, 结果表明, Pt纳米粒子为面心立方晶体结构, 均匀地分布在WO₃修饰的碳纳米管表面. 采用循环伏安(CV)和计时电流法研究了在酸性溶液中Pt-WO₃/CNT催化剂对甲醇的电催化氧化活性, 结果表明WO₃修饰的碳纳米管载铂催化剂比用混酸处理的碳纳米管载铂催化剂对甲醇呈现出更高的电催化氧化活性和更好的稳定性.     

Controllable fabrication of platinum nanospheres with a polyoxometalate-assisted process

Pt nanospheres with an average diameter of 60±10 nm have been successfully synthesized at room temperature through a facile polyoxometalate(POM)-assisted process. Characterization by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) clearly showed that these Pt nanospheres consisted of 2-7 nm Pt nanodots. During the formation of such unique nanostructures, POMs were found to serve as both catalyst and stabilizer. The size of the as-synthesized Pt nanospheres could be controlled solely by adjusting the molar ratio of POMs to H₂PtCl₆. A possible formation mechanism based on POMs-mediated electron transfer from ascorbic acid (AA) to PtCl₆²⁻ and AA-assisted aggregation was tentatively proposed to rationalize the formation of such nanostructures. Importantly, these specific Pt nanospheres exhibited good electrocatalytic activity towards the oxidation of methanol, making them promising for applications in direct methanol fuel cells.     

Preparation and Characterization of Polymer‐Protected Pt@Pt/Au Core‐Shell Nanoparticles

Poly(N‐vinyl‐2‐pyrolidone) protected Pt‐core bimetallic Pt/Au‐shell (Pt@Pt/Au) nanoparticles were prepared by multi‐step reduction of HAuCl₄ and H₂PtCl₆ alternately by hydrogen adsorbed on platinum atom. Transmission electronic microscopy (TEM) and x‐ray diffraction (XRD) were used to characterize Pt@Pt/Au nanoparticles. The structure of the shell of the nanoparticles seems to be the Au‐Pt solid solution.     

Solvent effect on the size of platinum nanoparticle synthesized in microemulsion systems

In this research work, the effect of solvent on the size of paltinum nanoparticles synthesized by microemulsion method was investigated. Platinum nanoparticles have been prepared by the reduction of H₂PtCl₆ with hydrazine in water-in-oil (w/o) microemulsions consisting of sodium bis(2-ethylhexyl) sulfo-succinate (AOT) and solvents n-hexane, cyclohexane and n-nonane. The size of the platinum nanoparticles was measured using transmission electron microscopy (TEM). It was verified that, for reduction of H₂PtCl₆ by hydrazine in microemulsion with different organic solvents, the solvents are arranged by their influence on nanoparticle sizes as follows: n-nonane > cyclohexane > n-hexane.     

Adsorption of PtCl62- anions on the surface of carbon black?

Summary Adsorption of PtCl₆^2- anions on surface of carbon black was studied. It was found that the absence of surface oxygen groups led to a higher Pt loading amount, and the Pt loading amount would decrease as using a higher H₂PtCl₆ impregnating solution concentration. The π sites in the basal planes of carbon black surface act as the chemical adsorption sites, playing a more important role than surface oxygen groups in PtCl₆^2- adsorption. Adsorption of large amounts of H₃O⁺ in the π sites would lead to a decrease of chemical adsorption capacity.     

Ordered mesoporous carbon decorated with rare earth oxide as electrocatalyst support for Pt nanoparticles

Ordered mesoporous carbon with large porosity was surface-modified with PrO_x and subsequently deposited with Pt nanoparticles by microwave heating. Transmission electron microscopy images indicated that PrO_x could improve the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt catalysts was evaluated according to hydrogen adsorption region of cyclic voltammograms and electrochemical impedance spectroscopy. Pt/C–PrO_x exhibited excellent performance in H₂SO₄, with a larger electrochemical active area and lower charge-transfer resistance than that of Pt/C. It is mainly due to enhanced dispersion of Pt nanoparticles and improved hydrogen adsorption on support.     

Synthesis of Platinum Nanoparticles-Decorated Poly(p-Phenylenediamine) Colloids with a High Performance for Methanol Electrocatalysis for Direct Methanol Fuel Cells

In this paper, the Pt/Poly(p-phenylenediamine) (Pt/PpPD) nanocomposite was synthesized via hydrothermal condition with H₂PtCl₆ as oxidant. The H₂PtCl₆ is an oxidant in formation process of PpPD and also played a role as the platinum source. The synthesis technique of this material is simple and the carrier material is low-cost. The spherical Pt nanoparticles which the diameter is about 50 nm are symmetrical dispersed on elliptical PpPD nanoparticles. The structure and morphologies of the composite were characterized with IR, Raman spectroscopy, XRD and scanning electron microscope. Electrocatalytic activity measurements shows the Pt/PpPD nanocomposite have good electrochemical performance for methanol fuel cells. The origin of good electrochemical performance for methanol of Pt/PpPD colloids is studied. The possible formation mechanism involved is also discussed.     

Effects of carbon surface oxides on the dispersion of Pt/C catalysts prepared via adsorption of hexachloroplatinic acid: a new insight

Summary A new concept is advanced to explain some effects of oxygen-containing groups of the carbon surfaces on the dispersion of Pt/C catalysts prepared through the adsorption of H₂PtCl₆ onto porous carbon powders followed by the reduction with H₂. These groups alter the electrochemical properties of the support and, therefore, influence the nature and amount of the adsorbed catalyst precursors formed during a redox reaction between the carbon surface and H₂PtCl₆, that reflects on the dispersion of Pt/C. A way to account for their impact on platinum dispersion is offered. It allows revising and uniting many literature data related to this problem.     

PtPd-nanoparticles supported by new carbon materials

Nanocomposites based on PtPd nanoparticles with chemical ordering like disordered solid solution on surface of multilayer graphene have been prepared through thermal shock of mechanically obtained mixture of double complex salt [Pd(NH₃)₄][PtCl₆] and different carbon materials–exfoliated graphite, graphite oxide and graphite fluoride. An effect of original carbon precursors on formation of PtPd bimetallic nanoparticles was studied using X-ray absorption spectroscopy (XAFS), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). It was shown that the distribution of bimetallic nanoparticles over the multilayer graphene surface as well as the particles size distribution is controlled by the graphene precursors. For all nanocomposites, the surface of the nanoparticles was found to be Pd-enriched. In case when the thermal exfoliated graphite and graphite oxide were used as the graphene precursors a thin graphitized layer covered the nanoparticles surface. Such a graphitized layer was not observed in the nanocomposite, which used the fluorinated graphite as the precursor.     

Pt and Pt–Ru nanoparticles decorated polypyrrole/multiwalled carbon nanotubes and their catalytic activity towards methanol oxidation

Conducting polymer composite films comprised of polypyrrole (PPy) and multiwalled carbon nanotubes (MWCNTs) [PPy–CNT] were synthesized by in situ polymerization of pyrrole on carbon nanotubes in 0.1 M HCl containing (NH₄)S₂O₈ as oxidizing agent over a temperature range of 0–5 °C. Pt nanoparticles are deposited on PPy–CNT composite films by chemical reduction of H₂PtCl₆ using HCHO as reducing agent at pH = 11 [Pt/PPy–CNT]. The presence of MWCNTs leads to higher activity, which might be due to the increase of electrochemically accessible surface areas, electronic conductivity and easier charge-transfer at polymer/electrolyte interfaces allowing higher dispersion and utilization of the deposited Pt nanoparticles. A comparative investigation was carried out using Pt–Ru nanoparticles decorated PPy–CNT composites. Cyclic voltammetry demonstrated that the synthesized Pt–Ru/PPy–CNT catalysts exhibited higher catalytic activity for methanol oxidation than Pt/PPy–CNT catalyst. Such kinds of Pt and Pt–Ru particles deposited on PPy–CNT composite polymer films exhibit excellent catalytic activity and stability towards methanol oxidation, which indicates that the composite films is more promising support material for fuel cell applications.     

Electrodeposition and electrocatalytic properties of platinum nanoparticles on multi-walled carbon nanotubes: effect of the deposition conditions

Platinum (Pt) nanoparticles were electrochemically deposited on multi-walled carbon nanotubes (MWCNTs) through a three-step process, including an electrochemical treatment of MWCNT, electro-oxidation of PtCl₄ ²⁻ to Pt(IV) complex, and an electro-conversion of Pt(0) on MWCNT. The effect of formation conditions for Pt(IV) complexes on the Pt nanoparticals transformed was investigated. The structure and elemental composition of the resulting Pt/MWCNT electrode were characterized by transmission electron micrograph (TEM) and energy dispersive X-ray spectroscopy (EDX). The electrocatalytic properties of the resulting Pt/MWCNT electrode for methanol oxidation have been investigated. The high electrocatalytic activity and good stability of Pt/MWCNT electrode may be attributed to the high dispersion of platinum nanoparticles and the particular properties of the MWCNT supports.     

Graphene–Pt nanocomposite for nonenzymatic detection of hydrogen peroxide with enhanced sensitivity

A sensitive hydrogen peroxide (H₂O₂) sensor was fabricated based on graphene–Pt (GN–Pt) nanocomposite. The GN–Pt was synthesized by photochemical reduction of K₂PtCl₄ on GNs, and characterized by atomic force microscope (AFM), transmission electron microscope (TEM), and energy-dispersive X-ray spectroscopy (EDS). Electrochemical investigations indicated that the GN–Pt exhibited a high peak current and low overpotential towards the reduction of H₂O₂. The GN–Pt modified glass carbon electrode displayed a wide linear range (2–710 μM), low limit of detection (0.5 μM) and good selectivity for detection of H₂O₂ with a much higher sensitivity than that of Pt nanoparticles or graphene modified electrode.     

Effects of heat treatment and poly(vinylpyrrolidone) (PVP) polymer on electrocatalytic activity of polyhedral Pt nanoparticles towards their methanol oxidation

In this paper, the polyhedral Pt nanoparticles under control were prepared by polyol method using AgNO₃ and poly(vinylpyrrolidone) (PVP) in the reduction of H₂PtCl₆ with ethylene glycol (EG). Transmission electron microscopy (TEM) and high resolution (HR) TEM measurements were used to investigate their characterization. In the case of the previous removal of PVP by washing and heating at 300°C, the specific morphologies of polyhedral Pt nanoparticles were still observed. However, the removal of PVP only by heat treatment at 300°C without washing causes the significant variation of their morphology. The large Pt particles were observed in the self-aggregation and assembly of the as-prepared polyhedral Pt nanoparticles. The pure Pt nanoparticles by washing and heat treatment showed the electrocatalytic property better than PVP-Pt nanoparticles by heat treatment due to the incomplete removal of PVP and by-products from AgNO₃. Therefore, the removal modes of PVP without changing their characterization are required to obtain the good catalytic performance.     

Green synthesis of nanowire-like Pt nanostructures and their catalytic properties

We reported a simple and effective green chemistry route for facile synthesis of nanowire-like Pt nanostructures at one step. In the reaction, dextran acted as a reductive agent as well as a protective agent for the synthesis of Pt nanostructures. Simple mixing of precursor aqueous solutions of dextran and K₂PtCl₄ at 80 °C could result in spontaneous formation of the Pt nanostructures. Optimization of the experiment condition could yield nanowire-like Pt nanostructures at 23:1 molar ratio of the dextran repeat unit to K₂PtCl₄. Transmission electron microscopy results revealed that as-prepared nanowire-like Pt nanostructures consisted of individual Pt nanoparticles with the size range from 1.7 to 2.5 nm. Dynamic light scattering analysis indicated that as-prepared nanowire-like nanostructures have already formed in solution. The as-prepared nanowire-like Pt nanostructures were further characterized by UV-vis spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. In addition, the ratio dependence and temperature dependence of this reaction have also been investigated. The as-prepared nanowire-like Pt nanostructures can be immobilized on glassy carbon electrodes using an electrochemical coupling strategy, and the resulting nanowire-like Pt nanostructures modified film exhibited an excellent electrocatalytic activity for the reduction of oxygen and the oxidation of NADH.     

The effect of electrochemically treated glassy carbon on the activity of supported Pt catalyst in methanol oxidation

Effect of electrochemical oxidation of glassy carbon on deposition of platinum particles and electrocatalytic activity of platinum supported on oxidized glassy carbon (Pt/GC_OX) were studied for methanol oxidation in H₂SO₄ solution. Platinum was potentiostatically deposited from H₂SO₄ + H₂PtCl₆ solution. Glassy carbon was anodically polarised in 0.5 M H₂SO₄ at 2.25 V vs. saturated calomel electrode (SCE) during 35 s. Electrochemical treatment of GC support, affecting not significantly the real Pt surface area, leads to a better distribution of platinum on the substrate and has remarkable effect on the activity. The activity of the Pt/GC_OX electrode for methanol oxidation is larger than polycrystalline Pt and for more than one order of magnitude larger than Pt/GC electrode. This increase in activity indicates the pronounced role of organic residues of GC support on the properties of Pt particles deposited on glassy carbon.