In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO.sub.2 and epoxides comprising 1) a catalyst including a metal coordination compound having a permanent ligand set and at least one ligand that is a polymerization initiator, and 2) a chain transfer agent having one or more sites capable of initiating copolymerization of epoxides and CO.sub.2, wherein the chain transfer agent contains one or more masked hydroxyl groups. In a second aspect, the present disclosure encompasses methods for the synthesis of polycarbonate polyols using the inventive polymerization systems. In a third aspect, the present disclosure encompasses polycarbonate polyol compositions characterized in that the polymer chains have a high percentage of OH end groups, a high percentage of carbonate linkages, and substantially all polycarbonate chains having hydroxyl end groups have no embedded chain transfer agent.

Methods, kits, cartridges, and compounds related to generating chlorine dioxide by exposing ClO.sub.2.sup. to at least one of a manganese porphyrin catalyst or a manganese porphyrazine catalyst are described. Methods, kits, cartridges, and compounds related to decomposed cyanide ions and hydrogen cyanide for water decontamination.

Methods, kits, cartridges and compounds related to generating chlorine dioxide by exposing ClO.sub.2.sup. to at least one of a manganese porphyrin catalyst or a manganese porphyrazine catalyst are described. Methods, kits, cartridges and compounds related to decomposed cyanide ions and hydrogen cyanide for water decontamination.

A zinc-based nanohybrid was prepared using a facile wet chemistry process. This nanohybrid has zinc oxide nanostructures connected to zinc phthalocyanine molecules via biologically important ligands. In addition, this nanohybrid has photocatalytic properties and photodegrades water pollutants, such as methyl orange.

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

Use of a unique supramolecular assembly of a tris-pyridylphosphine ligand and a metal centered porphyrin complex modified with a lactone functional group was shown to have improved selectivities to branched aldehydes via rhodium catalyzed hydroformylation of unsubstituted linear alpha olefins such as propylene and 1-octene. The addition of potassium salts was also shown to increase the activity of the lactone modified porphyrin-based catalyst while maintaining similar branched aldehyde selectivities for propylene hydroformylation.

Among other things, the present invention encompasses the applicant's recognition that epoxide carbonylation can be performed industrially utilizing syngas streams containing hydrogen, carbon monoxide and varying amounts carbon dioxide. Contrary to expectation, the epoxide carbonylation reaction proceeds selectively in the presence of these mixed gas streams and incorporates excess CO in the syngas stream into valuable chemical precursors, resulting in hydrogen streams substantially free of CO. This is economically and environmentally preferable to performing WSGR which releases the excess carbon as CO2. The integrated processes herein therefore provide improved carbon efficiency for processes based on coal or biomass gasification or steam methane reforming.

The present invention encompasses catalysts for the carbonylation of heterocycles such as ethylene oxide, as well as methods for their use. The catalysts feature Lewis acidic metal complexes having one or more tethered metal-coordinating groups in combination with at least one metal carbonyl species. In preferred embodiments, the inventive catalysts have improved stability when subjected to product separation conditions in continuous ethylene oxide carbonylation processes.

In one aspect, the present invention provides catalysts for the carbonylation of heterocycles. The inventive catalysts feature metal-ligand complexes having cationic functional groups tethered to the ligand, wherein the tethered cationic groups are associated with anionic metal carbonyl species. The invention also provides methods of using the inventive catalysts to affect the ring opening carbonylation of epoxides.

The present invention describes an electrochemical system (1) to electrochemically reduce carbon monoxide (CO) into liquid methanol and gaseous H.sub.2, comprising an electrochemical cell with an anodic compartment with an anode (2) with a current collector (2A), at least a catalyst to electrochemically oxidize H.sub.2O, and a cathodic compartment with a cathodic electrolyte solution comprising the solvent (3), and a cathodic supporting electrolyte, the solvent (3) being water at basic pH of between 10.5 and 13.5, the reagent CO; a cathode (4) which comprises, on a current collector (4A) which is electrochemically inert, at least a cobalt molecular catalyst (4B) to electrochemically reduce CO into liquid methanol and the gas H.sub.2, a power supply (5) providing the energy necessary to trigger the electrochemical reactions involving the reagent.