Colloidal carbon-supported

Colloidal carbon supported cobalt can be obtained by the impregnation-chemical reduction method. Colloidal carbon sphere (CCS) support is produced from hydrothermal treated glucose. Porous spheres had a 300 nm diameter where pore diameter and specific surface area were 5.7 nm and 20071 m g", respectively. Also metals had a nearly amorphous structure. Co layer was a uniform thin layer on CCS support. Maximum hydrogen production rate of 10.4 L min" observed for the hydrolysis... 

The liquid-phase oxidation of glycerol was carried out by using carbon-supported gold particles of different sizes (2.7 2 nm) which were prepared by a colloidal route [120]. Indeed, a particle-size effect was observed because the selectivity to glyceric acid was increased to 75% with smaller particle sizes (4)ptmimn = 3.7 nm). 

Xin and co-workers modified the alkaline EG synthesis method by heating the metal hydroxides or oxides colloidal particles in EG or EG/water mixture in the presence of carbon supports, for preparing various metal and alloy nanoclusters supported on carbon [20-24]. It was found that the ratio of water to EG in the reaction media was a key factor influencing the average size and size distribution of metal nanoparticles supported on the carbon supports. As shown in Table 2, in the preparation of multiwalled carbon nanotube-supported Pt catalysts... 

An important eonelusion was that the best catalyst is not the alloyed one as expected, nor the mixture of Pt/XC 72 and Ru/XC 72 powders, but one eonsisting of a dispersion of Pt colloid and Ru colloid on the same carbon support, i.e., the Pt + Ru/XC 72 eatalyst. The latter leads to higher current densities for the eleetro-oxidation of methanol than the other catalysts with the same atomic ratio for potentials lower than 0.5 V versus a reversible hydrogen electrode (RHE) (Fig. 11.3). This result... 

More recently the transformation of carbon-supported Pt colloids of approximately 1 nm diameter into Pt alloys has been reported, which seems to yield an even better catalyst, since the alloy particles—although coarser than the initial Pt particles—show improved catalytic activity and stability. It is not unlikely that from these alloys by in-situ oxidation transition-metal platinum bronzes like NLPt304 are formed, being the catalysts proper. 

However, TEM measurements performed on a Pt0 83Sn017/C (Figure 9.15) indicated that the increase of the metal loading on the carbon support led to the formation of a multimodal distribution of the particle size. Then, to overcome this problem, colloidal methods were also developed in our laboratory. 

One of the main advantage of this method is that it allows different possibilities of synthesis of metallic particles deposited on a carbon support (1) synthesis of the catalysts with a controlled atomic ratio by coreduction, which consists in mixing different metal salts before their reduction leading to colloid formation and deposition on carbon (2) synthesis of the catalysts with a controlled atomic ratio by codeposition, which consists in mixing colloids of different... 

Because carbon black is the preferred support material for electrocatalysts, the methods of preparation of (bi)metallic nanoparticles are somewhat more restricted than with the oxide supports widely used in gas-phase heterogeneous catalysis. A further requirement imposed by the reduced mass-transport rates of the reactant molecules in the liquid phase versus the gas phase is that the metal loadings on the carbon support must be very high, e.g., at least lOwt.% versus 0.1-1 wt.% typically used in gas-phase catalysts. The relatively inert character of the carbon black surface plus the high metal loading means that widely practiced methods such as ion exchange [9] are not effective. The preferred methods are based on preparation of colloidal precursors, which are adsorbed onto the carbon black surface and then thermally decomposed or hydrogen-reduced to the (bi)metallic state. This method was pioneered by Petrow and Allen [10], and in the period from about 1970-1995 various colloidal methods are described essentially only in the patent literature. A useful survey of methods described in this literature can be found in the review by Stonehart [11]. Since about 1995, there has been more disclosure of colloidal methods in research journals, such as the papers by Boennemann and co-workers [12]. 

PEM fuel cells use a solid proton-conducting polymer as the electrolyte at 50-125 °C. The cathode catalysts are based on Pt alone, but because of the required tolerance to CO a combination of Pt and Ru is preferred for the anode [8]. For low-temperature (80 °C) polymer membrane fuel cells (PEMFC) colloidal Pt/Ru catalysts are currently under broad investigation. These have also been proposed for use in the direct methanol fuel cells (DMFC) or in PEMFC, which are fed with CO-contaminated hydrogen produced in on-board methanol reformers. The ultimate dispersion state of the metals is essential for CO-tolerant PEMFC, and truly alloyed Pt/Ru colloid particles of less than 2-nm size seem to fulfill these requirements [4a,b,d,8a,c,66j. Alternatively, bimetallic Pt/Ru PEM catalysts have been developed for the same purpose, where nonalloyed Pt nanoparticles <2nm and Ru particles <1 nm are dispersed on the carbon support [8c]. From the results it can be concluded that a Pt/Ru interface is essential for the CO tolerance of the catalyst regardless of whether the precious metals are alloyed. For the manufacture of DMFC catalysts, in... 

Colloidal Pt/RuO c- (C5 0.4nm) stabilized by a surfactant was prepared by co-hydrolysis of PtCU and RuCls under basic conditions. The Pt Ru ratio in the colloids can be between 1 4 and 4 1 by variation of the stoichiometry of the transition metal salts. The corresponding zerovalent metal colloids are obtained by the subsequent application of H2 to the colloidal Pt/Ru oxides (optionally in the immobilized form). Additional metals have been included in the metal oxide concept [Eq. (10)] in order to prepare binary and ternary mixed metal oxides in the colloidal form. Pt/Ru/WO c is regarded as a good precatalyst especially for the application in DMECs. Main-group elements such as A1 have been included in multimetallic alloy systems in order to improve the durability of fuel-cell catalysts. PtsAlCo.s alloyed with Cr, Mo, or W particles of 4—7-nm size has been prepared by sequential precipitation on conductant carbon supports such as highly disperse Vulcan XC72 [70]. Alternatively, colloidal precursors composed of Pt/Ru/Al allow... 

At NEU, a series of electrocatalysts were synthesized based on classical colloidal sol synthesis techniques. These included platinum nickel/carbon (PtNi/C), platinum chromium/carbon (PtCr/C), and platinum cobalt/carbon (PtCo/C) together with the control Pt/C. All of the above electrocatalysts were prepared with 20% metal loading on carbon support (Vulcan XC-72, Cabot Corp). Ohmic corrected Tafel... 

The example shows that the three-step preparation procedure described above produces true nanocatalysts having naked metal particles of defined size deposited on the support surface. Generally, carbon-supported colloidal pre-catalysts are conditioned at 300 C. However, individual heating and gas flow conditions may be optimized for every catalyst system on the basis of TGA-MS analysis data. For example, the optimum temperatures for conditioning supported nanometaUic pre-catalysts having tetraoclylammonium or aluminum-organic protective shells are 280 °C and 250 G respectively [96, 126]. 

The current state of the art carbon supported electrocatalyst is made using variants of the colloidal approach. A common approach is to dissolve the metal salt solution in an appropriate solvent followed by reduction to form a colloid. A wide variety of recipes using reducing agents, organic stabilizers, or shell-removing approaches have also been developed in recent years. The patents most frequently referred to in this field are from United Technologies by Petrow and Allen.Sols of the metal are obtained for instance by an initial formation of a metastable platinum-sulfito complex, which is inert at ambient temperature but decomposes and produces the small Pt-crystallites at temperatures in excess of 60°C. Thus a relatively well-defined crystal size between 2 to 6 nm can be obtained. 

The synthesis methods used for the preparation of carbon supported PtRuMo nanoparticles could be classified as adsorption of metal colloids onto the carbon surface, or impregnation of carbon support with metals precursor solution. Additionally, the incorporation of the metals has been carried out in a (1) one step method or with simultaneous incorporation of the three metals, and in (2) two step methods or sequential incorporation of Mo and PtRu nanoparticles ... 

One step methods. PtRuMo/C catalysts obtained by the impregnation manner revealed that the addition of a relatively small amount of Mo results in an electrocatalyst with a higher activity in CO or methanol electrooxidation than with the PtRu/C system. Moreover, Benker et al studied the effect of molybdenum precursor, and the physico-chemical characterization indicated that only traces of molybdenum were present in the samples when Mo (CO) 6 was used for the synthesis, while ammonium molybdate was an appropriate precursor for the synthesis of PtRuMo/C catalysts. On the other hand, a colloidal method developed by Bonnemann et alP was used to prepare carbon supported PtRuMo nanoparticles and established that this method provided a better tool for synthesizing PtRuMo (1 1 1) nanoparticles deposited on a carbon substrate, being more... 

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