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Synthesis

Molybdate Dianion Traps Carbon Dioxide And Spits Out Formate

Simple, soluble molecular oxide serves as a model system for carbon dioxide fixation

by Stephen K. Ritter
February 17, 2014 | APPEARED IN VOLUME 92, ISSUE 7

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Credit: Ioana Knopf
09207-scicon-molybdenum.jpg
Credit: Ioana Knopf

Inexpensive reduction of carbon dioxide to useful chemical reagents would help put a dent in solving Earth’s overabundance problem with the greenhouse gas. Inorganic chemists have turned to the task of designing catalysts for the job, but most of these systems so far involve complex ligands that are costly to synthesize. Taking a simple approach, Ioana Knopf and Christopher C. Cummins of Massachusetts Institute of Technology and their colleagues have identified a soluble molybdate system unencumbered by organic ligands for easy reduction of CO2 (Chem. Sci. 2014, DOI: 10.1039/c4sc00132j). The team found that [MoO4]2– readily binds CO2 at room temperature to irreversibly form a monocarbonate complex. With excess CO2 the complex forms a dicarbonate species, which is the first structurally characterized transition-metal dicarbonate derived from CO2. The researchers also found that the monocarbonate reacts with triethylsilane to produce formate, HCO2, which is an important reagent in many chemical processes. “While many researchers spend considerable time designing elaborate ligand systems perfectly tuned both sterically and electronically for carbon dioxide fixation applications, this work represents a straightforward and beautifully simple approach to achieving the same sorts of transformations,” observes Christine M. Thomas of Brandeis University, whose group has developed CO2-reduction catalysts.

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Comments
Kirk J. Abbey (February 23, 2014 2:28 PM)
This looks good until one reads that triethylsilane is the required reducing agent. This requirement negates any benefit by not having to use organic ligands and all issues related to cost effectiveness.

According to Wikipedia, "Formate is reversibly oxidized by the enzyme formate dehydrogenase." This apparently only requires an acidic medium and a source of electrons. The trapping of CO2 by photosynthesis using biological means is, of course, Nature's solution to the problem. See the following:

http://www.netl.doe.gov/publications/proceedings/01/carbon_seq/p15.pdf

From Wikipedia, "Accelerating the uptake of CCS: Industrial use of captured carbon dioxide - Appendix E: CO2 for use in algae cultivation". Global CCS Institute and Parsons Brinckerhoff. Retrieved 2012-12-11.

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