Metal as heterogeneous catalysts

M. Boudart, Supported Metals as Heterogeneous Catalysts, the Science of Precious Metals Applications, International Precious Metals Institute, Allentown, PA, 1989. 

XJsorption of gases on to transition metal surfaces is important, and transition metals or alloys are often used as heterogeneous catalysts. 

Hardness on the Mohs scale is often above 8 and sometimes approaches 10 (diamond). These properties commend nitrides for use as crucibles, high-temperature reaction vessels, thermocouple sheaths and related applications. Several metal nitrides are also used as heterogeneous catalysts, notably the iron nitrides in the Fischer-Tropsch hydriding of carbonyls. Few chemical reactions of metal nitrides have been studied the most characteristic (often extremely slow but occasionally rapid) is hydrolysis to give ammonia or nitrogen ... 

Many organic electrode processes require the adsorption of the electroactive species at the electrode surface before the electron transfer can occur. This adsorption may take the form of physical or reversible chemical adsorption, as has been commonly observed at a mercury/water interface, or it may take the form of irreversible, dissociative chemical adsorption where bond fracture occurs during the adsorption process and often leads to the complete destruction of the molecule. This latter t q)e of adsorption is particularly prevalent at metals in the platinum group and accounts for their activity as heterogeneous catalysts and as... 

Nanosize particles (e.g., metals, semiconductors, etc.) are of continuing interest because they possess fascinating catalytic, electronic, and optical properties. Larger particles decorated with smaller nanoparticles on their surface are of interest because of their potential use as heterogeneous catalysts and their relevance in electronic and optical sensor applications as well as surface-enhanced Raman scattering [39,72-75]. 

Composites containing nanometer-sized metal particles of a controllable and uniform size in an insulating ceramic matrix are very interesting materials for use as heterogeneous catalysts and for magnetic and electronic applications. They show quantum size effects, particularly the size-induced metal-insulator transition (SIMIT) [1],... 

The addition of dopants is found to have beneficial effects. However, they are not restricted only to transition metals. The hydrogenation of acrylic acid can be promoted significantly by the addition of neodymium ions onto the palladium particles [142], The selective transformation of 3,4-dichloronitrobenzene to the corresponding aniline has been selected to test pre-prepared Pt hydrosols as heterogeneous catalyst precursors (see Figure 3.9) [143],... 

The olefinic C=C double bond is easy to reduce, under mild conditions, with most of the hydrogenation catalysts, with noble metals, with different forms of nickel as heterogeneous catalysts, with Rh, Pt, Co complexes and with Ziegler catalysts as homogeneous catalysts. In the hydrogenation of dienes and polyenes the selectivity is the most important issue, i.e. how can one double bond be saturated with retention of the other(s). When high selectivity is required, homogeneous catalysts are used. Nevertheless, as known, their separation from the reaction mixture is a difficult task. 

Colloidal nanoparticles can be employed as heterogeneous catalyst precursors in the same fashion as molecular clusters. In many respects, colloidal nanoparticles offer opportunities to combine the best features of the traditional and cluster catalyst preparation routes to prepare uniform bimetallic catalysts with controlled particle properties. In general, colloidal metal ratios are reasonably variable and controllable. Further, the application of solution and surface characterization techniques may ultimately help correlate solution synthetic schemes to catalytic activity. 

The basic concept is the intuition that, whether homogeneous or heterogeneous, catalysis is primarily a process controlled by a molecular phenomenon since it implies the catalyzed transformation of molecules into other molecules. It follows that on the surface of metals or metal oxides, sulfides, carbides, nitrides usually involved as heterogeneous catalysts, the relevant surface species and the mechanism of their mutual reactions must be of molecular character, as occurs in homogeneous or enzymatic catalysis. 

Within a discussion of nanostructured catalysts, mention must be made of zeolitic systems. Zeolites are a broad family of natural and synthetic aluminosiU-cates that exhibit two important properties that makes them ideal for consideration as heterogeneous catalysts they are crystalline and porous. Crystallinity brings with it precise definition at the atomic scale that is absent with amorphous or polycrystaUine metal oxides. The combination of a well-defined structure and... 

Further evidence has been obtained to support the contention that the active catalysts are metal complexes dissolved in solution. With experiments reported in Table II, the kinetics of oxidation under standard conditions in the presence of various metal salts are compared with the rates of reaction when solid residues have been filtered from solution. The agreement between the rates in Cases 1 and 3 of Table II (where the amount of metal available is dictated by the solubility of metal complexes) shows that solid precipitates play little or no part in catalysis in all the systems studied. The amount of metal in solution has been measured in Cases 2 and 3 metal hydroxide complexes (Case 2) are not as soluble as metal-thiol complexes, and neither is as soluble as metal phthalocyanines (19). The results of experiments involving metal pyrophosphates are particularly interesting, in that it has previously been suggested that cobalt pyrophosphates act as heterogeneous catalysts. The result s in Table II show that this is not true in the present system. 

Table 4.1. Support-bound transition metal complexes as heterogeneous catalysts.

The transition metals iron and copper have been known since antiquity and have played an important role in the development of civilization. Iron, the main constituent of steel, is still important as a structural material. Worldwide production of steel amounts to some 800 million tons per year. In newer technologies, other transition elements are useful. For example, the strong, lightweight metal titanium is a major component in modern jet aircraft. Transition metals are also used as heterogeneous catalysts in automobile catalytic converters and in the industrial synthesis of essential chemicals such as sulfuric acid, nitric acid, and ammonia. 

Heterometal alkoxide precursors, for ceramics, 12, 60-61 Heterometal chalcogenides, synthesis, 12, 62 Heterometal cubanes, as metal-organic precursor, 12, 39 Heterometallic alkenes, with platinum, 8, 639 Heterometallic alkynes, with platinum, models, 8, 650 Heterometallic clusters as heterogeneous catalyst precursors, 12, 767 in homogeneous catalysis, 12, 761 with Ni—M and Ni-C cr-bonded complexes, 8, 115 Heterometallic complexes with arene chromium carbonyls, 5, 259 bridged chromium isonitriles, 5, 274 with cyclopentadienyl hydride niobium moieties, 5, 72 with ruthenium—osmium, overview, 6, 1045—1116 with tungsten carbonyls, 5, 702 Heterometallic dimers, palladium complexes, 8, 210 Heterometallic iron-containing compounds cluster compounds, 6, 331 dinuclear compounds, 6, 319 overview, 6, 319-352... 

Of course, metal-based heterogeneous catalysts for hydrogenation with molecular H2 or oxidation with 02 offer several advantages from the practical and environmental point of view, as they minimize wastes and reduce the work-up procedures. 

Fig. 17 a, b. Photosensitized H2-evolution systems a) basic configuration including a photosensitizer, S, an electron acceptor, A, and electron donor, D, and H2-evolution catalyst, b) H2-evolution system including MV2+ as electron acceptor and a noble metal colloid as heterogeneous catalyst... 

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