Pt-based catalyst

In 1993, UOP commercialized an improved Pt-based catalyst, 1-210. This catalyst is based on a molecular sieve, but not an alurninosihcate zeoHte. UOP claims that yields ate about 10% better than those for 1-9 catalyst. EB to xylenes conversion is about 22—25% with a Cg aromatics per pass loss of about 1.2—1.5%. As discussed below, UOP s Isomar process can also use zeoHte catalysts which convert EB to benzene rather than to xylenes. UOP has hcensed over 40 Isomar units. 

The small metal particle size, large available surface area and homogeneous dispersion of the metal nanoclusters on the supports are key factors in improving the electrocatalytic activity and the anti-polarization ability of the Pt-based catalysts for fuel cells. The alkaline EG synthesis method proved to be of universal significance for preparing different electrocatalysts of supported metal and alloy nanoparticles with high metal loadings and excellent cell performances. 

Au/C was established to be a good candidate for selective oxidation carried out in liquid phase showing a higher resistance to poisoning with respect to classical Pd-or Pt-based catalysts [40]. The reaction pathway for glycerol oxidation (Scheme 1) is complicated as consecutive or parallel reactions could take place. Moreover, in the presence of a base interconversion between different products through keto-enolic equilibria could be possible. 

In order to establish a clear strategy, we have examined the properties of Pt-based catalysts for both the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) systematically and comprehensively using various techniques, the results of which complement each other. We have also developed a standard method to evaluate the real activity. In this chapter, we summarize our recent research results. 

Finally, trimetallic compounds have been developed to enhance the electroactivity of Pt-based catalysts, for either methanol or ethanol electro-oxidation. A long time ago, it was reported that adsorption of molybdates (Na2Mo04) at a Pt black electrode... 

Such bimetallic alloys display higher tolerance to the presence of methanol, as shown in Fig. 11.12, where Pt-Cr/C is compared with Pt/C. However, an increase in alcohol concentration leads to a decrease in the tolerance of the catalyst [Koffi et al., 2005 Coutanceau et ah, 2006]. Low power densities are currently obtained in DMFCs working at low temperature [Hogarth and Ralph, 2002] because it is difficult to activate the oxidation reaction of the alcohol and the reduction reaction of molecular oxygen at room temperature. To counterbalance the loss of performance of the cell due to low reaction rates, the membrane thickness can be reduced in order to increase its conductance [Shen et al., 2004]. As a result, methanol crossover is strongly increased. This could be detrimental to the fuel cell s electrical performance, as methanol acts as a poison for conventional Pt-based catalysts present in fuel cell cathodes, especially in the case of mini or micro fuel cell applications, where high methanol concentrations are required (5-10 M). 

Nappom WT, Laborde H, Leger J-M, Lamy C. 1995. Flectro-oxidation of Ci molecules at Pt-based catalysts highly dispersed into a polymer matrix Effect of the method of preparation. J Electroanal Chem 404 153-159. 

The reductive alkylation of DAP with acetone led to high conversions and selectivity to the dialkylated product over Al, Bl, and BS2 catalysts. The ASl catalyst, which typically has lower activity than the Al or Pt-based catalysts showed greater formation of heterocycles. These results indicate that a more active catalyst, a shorter reaction time, a higher operating temperature, or sterically hindered amines/ketones will help minimize the formation of the heterocycles. Similar high selectivities were obtained with DAP-MIBK reaction over BSl and BS2 catalysts with no heterocycles being formed. However, over Al, the undesired heterocyclic compound was over 15%. This indicates that the reaction between diamines and ketones has a significant potential to form heterocyclic compounds unless the interaction between these is kept to a minimum by the use of a continuous flow reactor as proposed by Speranza et al. (16) or by other methods. 

A particular attention on the mechanisms for the formation of N20 over noble metals has been paid in our laboratory [37-40]. It was previously found that an enhancement in the initial selectivity towards the production of N2 (Table 10.1) during the CO + NO reaction can be related to an increase in the relative rate of step (13) over supported Pt-based catalysts [33], Unexpectedly, Rh exhibits a poor selectivity towards the formation of N2 at low conversion and low temperature, which has been mainly related to a stronger NO adsorption on Rh than on Pt and Pd. 

Table 10.1. Selectivity towards the formation of nitrogen on supported Pt-based catalysts at 300°C (initial partial pressure of NO and CO equal to 5 x 10 3 atm [37])...

Burch, R., Fornasiero, P. and Southward, B.W.F. (1999) An investigation into the reactivity, deactivation and in situ regeneration of Pt-based catalysts for the selective reduction of NOx under lean burn conditions, J. Catal. 182, 234. 

Another important catalytic technology for removal of NOx from lean-burn engine exhausts involves NOx storage reduction catalysis, or the lean-NOx trap . In the lean-NOx trap, the formation of N02 by NO oxidation is followed by the formation of a nitrate when the N02 is adsorbed onto the catalyst surface. Thus, the N02 is stored on the catalyst surface in the nitrate form and subsequently decomposed to N2. Lean NOx trap catalysts have shown serious deactivation in the presence of SOx because, under oxygen-rich conditions, SO, adsorbs more strongly on N02 adsorption sites than N02, and the adsorbed SOx does not desorb altogether even under fuel-rich conditions. The presence of S03 leads to the formation of sulfuric acid and sulfates that increase the particulates in the exhaust and poison the active sites on the catalyst. Furthermore, catalytic oxidation of NO to N02 can be operated in a limited temperature range. Oxidation of NO to N02 by a conventional Pt-based catalyst has a maximum at about 250°C and loses its efficiency below about 100°C and above about 400°C. 

This reaction is endothermic and is favored by low pressure. In practice, however, the process is conducted at a pressure of 1-3 MPa (because of a concurrent hydrocracking reaction) and a temperature of 300-450°C using Pt-based catalysts [7]. The feedstock for the reforming process must be carefully purified from S- and N-compounds (below 1 ppm), which may use up a significant portion of hydrogen produced. The typical composition of the off-gas from the catalytic reforming of naphtha is as follows (vol%) H2—82, CH4—7, C2—5, C3—4, and C4—2 [7]. 

Before preparing these carbon-supported Pt-based catalysts, a support pretreatment toward granular activated carbon with an aqueous solution of NaOH (pH 14) was carried out by immersing for 24 h to promote the anion exchange between the ligand chloride of impregnated metal precursers (K2PtCl4) and the aqueous hydroxide ion (OH ) inside the micropores of the activated carbon [33]. 

These observations can be explained taking into consideration that in this study the metal particle sizes were relatively large in all three catalysts, so the dicarbene mechanism dominated, even on the Pt-based catalysts. In any case, a somewhat higher selectivity towards substituted C-C cleavage was observed on the Pt catalysts, relative to the monometallic Ir catalyst. However, as we have recently pointed out, unless the naphthenic rings are opened very selectively at the substituted C-C bonds, no considerable gain in CN can be achieved by RO. This was not the case in any of the Pt-Ir catalysts presented in ref. 111. 

Dendrimer templated Pt-Au catalysts are also active for the selective catalytic reduction of NO by propylene in the presence of excess O2. In addition to its commercial importance, this reaction is particularly interesting for the Pt-Au system. Previous work with cluster-derived Pt-Au catalysts has demonstrated that this reaction exhibits structure sensitivity, suggesting that it may be possible to use it as a structural probe for Pt based catalysts. ... 

Supported noble metals such as Au and Pt are active for CO oxidation. Since Pt-based catalysts operate at relatively higher reaction temperatures (403 to 473 K), they are not very selective for CO oxidation in hydrogen-rich streams. Au catalysts. 

Spray pyrolysis routes have been extensively investigated to prepare Pt-based catalysts. Typically, a liquid feed of metal precursor and carbon is atomized into an aerosol and fed into a continuous furnace to evaporate and heat-treat to form a collectable powder. The method has good control over final aggregate particle size and metal particle size distributions, as well as producing powder without further isolation or separation. Hampton-Smith et al. have reviewed efforts of Superior MicroPowder (now Cabot Fuel Cells) in this area. ... 

In recent times, efforts have been made to optimize PtRu tolerance through the addition of third and fourth metals, as well as to identify alterative Pt-based catalysts with much greater reformate tolerance, particularly at much higher CO levels. Many of fhe reporfed sfudies are concerned with CO rather than reformate tolerance, and few long-ferm sfabilify measurements have been reported. 

Characterization of Pt-Based Catalysts byXPS and EXAFS/XANES... 

Commonly, transition metals on non-reducible supports are used for the selective hydrogenation of aromatic ketones, with most research to date having been done on Pt-based catalysts. In particular, we will discuss here some interesting results published on this subject. 

The investigation of new electrocatalysts, particularly Pt-based catalysts, that are more active for oxygen reduction and fuel oxidation (hydrogen from reformate gas or alcohols) is thus an important point for the development of PEMFCs [16,17, 22, 23]. 

In the case of ethanol, Pd-based electrocatalysts seem to be slightly superior to Pt-based catalysts for electro-oxidation in alkaline medium [87], whereas methanol oxidation is less activated. Shen and Xu studied the activity of Pd/C promoted with nanocrystalline oxide electrocatalysts (Ce02, C03O4, Mn304 and nickel oxides) in the electro-oxidation of methanol, ethanol, glycerol and EG in alkaline media [88]. They found that such electrocatalysts were superior to Pt-based electrocatalysts in terms of activity and poison tolerance, particularly a Pd-NiO/C electrocatalyst, which led to a negative shift of the onset potential ofthe oxidation of ethanol by ca 300 mV compared... 

Karski and co-workers found that thallium acts also as a promoter and prevents the poisoning of the palladium particle with oxygen. Indeed, a bimetallic system which contained 5 wt% of Th led to 100% selectivity to gluconic acid at 95% conversion [117]. On their side, Boimeman et al. reported that charcoal-supported Pd-Pt catalysts prepared from a colloidal solution of Pd-Pt/NOct4Cl exhibit a superior activity and selectivity than industrial heterogeneous Pd-Pt-based catalysts [118]. 

Nitrides and oxynitrides represent a relatively new class of catalytic material. Justin Hargreaves and D. McKay (University of Glasgow, UK) show that these materials have only recently been explored for reactions (e.g., photocatalysis) beyond those that take advantage of their acid-base properties and their ability to mimic Pt-based catalysts. Tuning the acid-base properties of nitrides is possible by incorporating oxygen within their structure. 

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