A practical, inexpensive, green chemical process for degrading environmental pollutants is greatly needed, especially for persistent chlorinated pollutants. Here we describe the activation of hydrogen peroxide by tetraamidomacrocylic ligand (TAML) iron catalysts, to destroy the priority pollutants pentachlorophenol (PCP) and 2,4,6-trichlorophenol (TCP). In water, in minutes, under ambient conditions of temperature and pressure, PCP and TCP are completely destroyed at catalyst:substrate ratios of 1:715 and 1:2000, respectively. The fate of about 90% of the carbon and about 99% of the chlorine has been determined in each case. Neither dioxins nor any other toxic compounds are detectable products, and the catalysts themselves show low toxicity.
By learning how to balance natural resource limitations and pollution prevention with economic growth, green chemistry will become the central science of sustainability. The elimination of persistent pollutants is vital for a sustainable civilization. To achieve this, the most important guiding concept is that the elemental composition of technology should be shifted toward the elemental composition of biochemistry. Oxidation chemistry is currently a prolific producer of persistent pollutants. Many arise from the use of chlorine, hypochlorite, or chlorine dioxide in large-scale oxidation processes. Oxidation chemistry can be greened by replacing these with catalyzed alternatives based on Nature's oxidizing agent, hydrogen peroxide. TAML® (TetraAmidoMacrocyclicLigand) iron catalysts, which were invented at Carnegie Mellon University, are widely patented and are being developed to activate H2O2 for commercial applications. TAML activators are water-soluble, easy to use, function well from neutral to basic pH, are not dominated by nonselective Fenton-like reactivity, are straightforward to synthesize, work effectively in minute concentrations, enable peroxide processes to occur at temperatures well below those of the processes targeted for replacement, and are amenable to modification for capturing novel selectivities. TAML activators are "dial-a-lifetime" catalysts: an activator can be chosen exhibiting a lifetime commensurate with the desired task.
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