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A metal-free, sustainable approach to CO2 reduction

Researchers in Japan are presenting an organic catalyst for CO2 reduction that is inexpensive, readily available and recyclable. As the level of catalytic activity can be tuned by the solvent conditions, their findings could open up many new directions for converting CO2 to industrially useful organic compounds.

Sustainability is a key goal in the development of next-generation catalysts for CO2 reduction. One promising approach that many teams are focusing on is a reaction called the hydrosilylationof CO2; catalytic hydrosilation is used to prepare organosilicon compounds and involves the addition of silicon–hydrogen bonds across unsaturated bonds.

However, most catalysts developed to date for this purpose have the disadvantage of containing metals that are expensive, not widely available and potentially detrimental to the environment.

Now, scientists at Tokyo Institute of Technology (Tokyo Tech) and the Renewable Energy Research Center at Japan's National Institute of Advanced Industrial Science and Technology (AIST) have demonstrated the possibility of using a fully recyclable, metal-free catalyst.

By comparing how well different organic catalysts could achieve hydrosilylation of CO2, the team identified one that surpassed all others in terms of selectivity and yield. This catalyst, called tetrabutylammonium (TBA) formate, achieved 99% selectivity and produced the desired formate product with a 98% yield. The reaction occurred rapidly (within 24 hours) and under mild conditions, at a temperature of 60 ˚C.

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Formate-catalyzed reduction of CO2 to formate products. Representation of the process whereby formate salts serve as active and selective catalysts for the hydrosilylation of CO2.


The catalyst has a turnover number of up to 1,800—more than an order of magnitude higher than previous results.

In 2015, team leader Ken Motokura of Tokyo Tech’s Department of Chemical Science and Engineering and his colleagues found that formate salts show promising catalytic activity. It was this hint that provided the basis for the current study.

Although we did expect formate salts to exhibit good catalytic activity, TBA formate showed much higher selectivity, stability and activity that went beyond our expectations.

—Ken Motokura

In the current study, the researchers found that the catalyst can be made reusable by using toluene as a solvent. They showed that Lewis basic solvents such as N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO) can accelerate the reaction, meaning that the catalytic system is tunable.

Overall the findings, published in the online edition of the journal ACS Sustainable Chemistry & Engineering, offer a new, environmentally friendly path to reducing CO2 at the same time as yielding industrially important formate products.

Silyl formate can be easily converted to formic acid, which can serve as an important hydrogen carrier, for example, in fuel cells. The high reactivity of silyl formate enables its conversion into intermediates for the preparation of organic compounds such as carboxylic acids, amides and alcohols.

This efficient transformation technique of CO2 to silyl formate will expand the possibilities for CO2 utilization as a chemical feedstock.

—Ken Motokura

The study was supported by a Japan Society for the Promotion of Science (JSPS) Grant-in-Aid for Scientific Research on Innovative Areas and is an exemplary model of the AIST–Tokyo Tech cross-appointment system.

Resources

  • Ken Motokura, Chihiro Nakagawa, Ria Ayu Pramudita, and Yuichi Manaka (2019) “Formate-Catalyzed Selective Reduction of Carbon Dioxide to Formate Products Using Hydrosilanes” ACS Sustainable Chem. Eng. doi: 10.1021/acssuschemeng.9b02172

Comments

Engineer-Poet

I'm suprised to see 24 hours described as "rapid".  Holding an inventory of 24 hours worth of CO2 generation from e.g. a power plant would require enormous volumes.

Other than that, I wonder if this process is selective for CO2.  If the species involved do not react with e.g. methane, this might be usable as a way to separate and capture CO2 from streams like biogas and landfill gas.

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