Noble metal ionic catalysts.

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NO(x), and unburned hydrocarbons-need to be fully converted to CO(2), N(2), and H(2)O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al(2)O(3) or SiO(2) promoted by CeO(2). However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce(1-x)M(x)O(2-delta) and Ce(1-x-y)Ti(y)M(x)O(2-delta) (M = Pt, Pd, Rh; x = 0.01-0.02, delta approximately x, y = 0.15-0.25) oxides in fluorite structure. In these oxide catalysts, Pt(2+), Pd(2+), or Rh(3+) ions are substituted only to the extent of 1-2% of Ce(4+) ion. Lower-valent noble metal ion substitution in CeO(2) creates oxygen vacancies. Reducing molecules (CO, H(2), NH(3)) are adsorbed onto electron-deficient noble metal ions, while oxidizing (O(2), NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NO(x) reduction (with >80% N(2) selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO(2) or Ce(1-x)Ti(x)O(2) were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO(2) lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M(0)/M(n+), Ce(4+)/Ce(3+), and Ti(4+)/Ti(3+) redox couples leads to the promoting action of CeO(2), activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

Hydrazinium thiocyanate as a reagent for determination of copper.

Hydrazinium thiocyanate, N(2)H(5)SCN, has been used for the determination of copper in copper salts. The reagent reduces the copper ions to the cuprous state and precipitates cuprous thiocyanate Cu(2)(SCN)(2), quantitatively.

Formation of "photodieldrin" by microorganisms.

Photodieldrin, previously reported as the major conversion product of dieldrin by sunlight, was found among the metabolic products of dieldrin among microorganisms isolated from various environments including soil, water (Lake Michigan), rat intestines, and rumen stomach contents of a cow.

Degradation of endrin, aldrin, and DDT by soil microorganisms.

Twenty microbial cultures which had been shown to degrade dieldrin were tested to determine their ability to degrade endrin, aldrin, DDT, gamma isomers of benzenehexachloride (gamma-BHC), and Baygon. All isolates were able to degrade DDT and endrin, whereas 13 degraded aldrin. However, none of them was able to degrade Baygon or gamma-BHC.

Adenosine triphosphatase. Sensitive to DDT in synapses of rat brain.

The insecticide DDT selectively inhibits the action of a Na(+), K(+), Mg(2+)-adenosine triphosphatase found in the nerve ending fraction of the rat brain. As judged by the concentrations of inhibitors that give 50 percent of enzyme inhibition, DDT was approximately 1000 times more toxic than its non-insecticidal analog, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene. The degrees of inhibition of this enzyme system by various toxic and nontoxic DDT analogs were closely related to a general toxicity in vivo of these compounds. Moreover, the extents of inhibition of this enzyme system by DDT were much higher at low temperatures, an indication of a causal relation between poisoning in vivo by DDT and the inhibition in vitro of the Na(+), K(+), Mg(2+)-adenosine triphosphatase system.