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Multicomponent catalytic system efficiently converts carbon dioxide to methanol

Inspired by naturally occurring processes, a team of Boston College chemists used a multi-catalyst system to convert carbon dioxide to methanol at the lowest temperatures reported with high activity and selectivity. A paper on the work is published in the journal Chem.

Methanol is a promising renewable fuel that can be adapted to the current liquid fuel infrastructure. It can be produced from hydrogen and carbon dioxide, mitigating greenhouse gas emissions and storing hydrogen in the process. However, the industrial production of methanol through this hydrogenation reaction currently requires elevated temperatures and pressures and can produce significant amounts of unwanted byproducts.

Here, we employ a bioinspired tandem catalytic system to efficiently hydrogenate carbon dioxide to methanol selectively at low temperatures. We achieved superior performance by eliminating catalyst incompatibility through encapsulating at least one of the catalysts involved in the tandem process in nanoporous materials called metal-organic frameworks. In the long term, this method could be applied to other tandem catalytic processes, allowing more efficient access to alternative fuels, commodity chemicals, and valuable pharmaceutical products.

—Rayder et al.

The team’s discovery was made possible by installing multiple catalysts in a single system constructed within a sponge-like porous crystalline material known as a metal-organic framework, said Boston College Associate Professors of Chemistry Jeffery Byers and Frank Tsung, lead authors of the report.

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Boston College researchers used three different catalysts in one system to transform, in three steps, the greenhouse gas carbon dioxide to methanol, a liquid fuel that serves as a promising method for hydrogen storage. The first catalyst converts carbon dioxide and hydrogen to formic acid, which is then modified by a second catalyst to form an ester, incorporating an alcohol additive and producing water. The third catalyst in the system, which is typically incompatible with the first catalyst, then converts this ester to methanol. The team was able to perform this multistep reaction in one reaction vessel despite using two incompatible catalysts by encapsulating one in a porous framework that also acts as the second catalyst. Credit: Frank Tsung


Held in place by the sponge, the separate catalysts work in harmony. Without isolation of the catalytically active species in this way, the reaction did not proceed and no product was obtained, they reported.

The team drew its inspiration from the biological machinery in cells, which use multicomponent chemical reactions with great efficiency, Tsung said.

The team employed catalyst separation through host-guest chemistry—where a “guest” molecule is encapsulated in a “host” material to form a new chemical compound—in order to convert carbon dioxide to methanol. The approach, inspired by the multicomponent catalytic transformations in nature, converted a greenhouse gas to a renewable fuel while avoiding high catalytic demand on a single species.

We accomplished this by encapsulating one or more catalysts in metal-organic framework and applying the resulting host-guest construct in catalysis in tandem with another transition metal complex.

—Frank Tsung

The team, which included graduate student Thomas M. Rayder and undergraduate Enric H. Adillon, set out to determine whether they could develop an approach to integrate incompatible catalysts in order to convert carbon dioxide to methanol at low temperature and with high selectivity, said Byers.

Specifically, they wanted to find out if there are specific advantages to this approach when compared to current state-of-the-art systems for transition metal complex-based conversion of carbon dioxide to methanol.

Positioning multiple transition metal complex catalysts at the right position in a system is critical to the reaction turning over. At the same time, encapsulating these catalysts allowed for recyclability in the multicomponent catalytic system.

—Jeffery Byers

These properties make the multicomponent catalyst construct more industrially relevant, which may pave the way for a carbon-neutral fuel economy, the researches said.

In addition to achieving site isolation by encapsulating the catalysts, which led to catalyst activity and recyclability, the team discovered an autocatalytic feature of the catalyst that enabled the reaction to be run without the need for large amounts of additives. Most previous reports for similar reactions use large amounts of additives, but the team’s approach avoids this necessity.

The team plans to do further research into the modularity of both the encapsulation method and the metal-organic frameworks to gain a deeper understanding of the multicomponent system and optimize it further, as well as access new, unexplored reactivity through the formation of new host-guest constructs, Tsung said.

Resources

  • Thomas M. Rayder, Enric H. Adillon, Jeffery A. Byers, Chia-Kuang Tsung (2020) “A Bioinspired Multicomponent Catalytic System for Converting Carbon Dioxide into Methanol Autocatalytically,” Chem, Volume 6, Issue 7, Pages 1742-1754, doi: 10.1016/j.chempr.2020.04.008

Comments

WillyG

I wonder how practical the scale up of this process will be. It sounds like it might be a big step forward for RE fuels. Nice!

mahonj

Lets hope it works out.
methanol is a very good way of moving H2 about.
It would be great if we could produce it efficiently.
At least it is a liquid, not a gas.
And with work, you might be able to make Ethanol or propanol which would have lower boiling points, etc.

SJC_1

20+ billion gallons of methanol use used each year worldwide.
The MTG process can make synthetic gasoline.

Marcel Williams

Natural gas electric power plants can be easily and cheaply modified to use methanol which produces electricity more efficiently than natural gas.

Several ocean vessels have been modified to use methanol which is a much cleaner marine fuel.

Methanol can be converted into gasoline and into various types of jet fuel.

Methanol can be converted into dimethyl ether-- a diesel fuel alternative for trucks and construction and farm vehicles.

Plug-in-hybrid methanol fuel cell vehicles would have superior performance relative to purely electric automobiles and should be much cheaper since they don't require as many batteries. They could also be utilized to power your home during a power outage-- almost indefinitely-- as long as you access to bottles of methanol.

SJC_1

Welcome Marcel,
I have been saying those same solutions for years :)

ElectrikLeo

Still means we'll be breathing poison.......

mahonj

@ELow, what poison are you referring to - CO2 or MeOH ?
CO2, while causing greenhouse warming is not a poison for humans at levels under 5-10%, and we are at 440 ppm so we are miles away for that.

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5380556/#:~:text=CO2%20toxicity%20in%20humans&text=Concentrations%20of%20more%20than%2010,loss%20of%20consciousness%20in%20seconds.

Methanol is poisonous when drunk rather than breathed in.
I don't quite follow your comment.

SJC_1

People using hand sanitizer with methanol many times a day for months can absorb some, you won't get a toxic dose filling your fuel tank once a week.

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