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Oxford Researchers Developing Method for Homogeneous Conversion of CO2 to Methanol Under Relatively Mild Conditions and Without Metal Catalysts

CO2 was converted into methanol by adding it to frustrated Lewis Pairs in toluene under H2, heating the mixture, and vacuum distillation. Credit: Angewandte Chemie. Click to enlarge.

Researchers at the University of Oxford are developing a method for the homogeneous conversion of CO2 to methanol (i.e., methanol is the only resulting C1 product) for use as a fuel using a “frustrated Lewis Pair” (FLP)-based nonmetal-mediated procedure at pressures of 1–2 atm and 160 °C. A paper on their work was published in the 21 December 2009 issue of the journal Angewandte Chemie International Edition.

Current approaches to hydrogenating CO2 to CH3OH (methanol)—a reaction that is themodynamically favorable, “but...not the most favorable transformation of CO2 with H2”, the authors note—rely on solid oxide catalysts.

However, these systems tend to give mixtures of C1 products: CO, CH3OH, and CH4. Furthermore, we are not aware of the homogeneous conversion of CO2 into CH3OH with nonmetal complexes...Herein we describe the heterolytic activation of hydrogen and subsequent insertion of CO2 into a B-H bond in the first homogeneous process for the conversion of CO2 into methanol.

—Ashley et al.

A frustrated Lewis pair (FLP) is a Lewis acid - base pair in which steric hindrance (which occurs when the size of groups within a molecule prevent chemical reactions that occur in related smaller molecules) precludes the formation of a regular Lewis acid-base adduct (a molecule formed by the direct addition of two or more distinct molecules) formation—as in ammonia borane. Kept from the “normal” reaction, these “frustrated” groups turn to other molecules.

Other research groups have shown that FLPs can activate H2 heterolytically (cleaving a chemical bond). These systems can be used in metal-free catalytic hydrogenation and addition to olefins and other organic substrates.

Andrew E. Ashley, Amber L. Thompson, and Dermot O’Hare used a FLP consisting of the base tetramethylpiperidine (TMP) and the acid B(C6F5)3, which had been shown in other work to cleave hydrogen (H2) to form the salt [TMPH] [HB(C6F5)3].

...upon the addition of CO2 (1 equiv) to a 1:1 mixture of TMP/B(C6F5)3 (4 equiv) in C7D8 under an H2 atmosphere, quantitative conversion into CH3OB(C6F5)2 via 2 was observed after 6 days at 160 °C. Remarkably, vacuum distillation of the solvent (100 °C) led to the isolation of CH3OH (17–25% yield based on integration of the 1H NMR spectrum against internal Cp2Fe and GC analysis) as the sole C1 product, alongside C6F5H and TMP by-products. We expect that the formation of methanol results from the reaction of CH3OB(C6F5)2 with TMP or its conjugate acid.

...Current investigations are focused on increasing the stability of the system towards hydroxylic agents with the hope of thereby rendering the system catalytic.

—Ashley et al.


  • Andrew E. Ashley, Amber L. Thompson, Dermot O’Hare (2010) Non-Metal-Mediated Homogeneous Hydrogenation of CO2 to CH3OH. Angewandte Chemie International Edition Volume 48 Issue 52, Pages 9839 - 9843 doi: 10.1002/anie.200905466



Take the CO2 and combine it with H2 from a concentrated solar thermal PV and you have methane. Reversible SOFCs with multiple juction PV can create the hydrogen efficiently using the heat and light and there is an abundance of CO2 at ethanol distilleries.

"pressures of 1–2 atm and 160 °C..."

These really are mild conditions that can be created from the concentrated solar as well. If you can not run your car from solar panels then you can use the sun to make methanol for your PHEV FFV. As one clever person put it, it will be a "methanol economy". Or we will be in a bind and cause ourselves even more hardship.

Henry Gibson

Yes CO2 recycling with hydrogen will be a good source of liquid fuel when nuclear hydrogen becomes available as is happening soon in France. This recycling has even been shown to be done by organisms that produce ethanol. In any case, large scale chemical processes work sufficiently well. The prodution of CO2 is lowered now if any hydrogen from non petroleum sources is added to crude oil during the refining process. Even the use of hydrogen from natural gas (methane) saves the production of CO2.

It must be said that hydrogen produced from spare nuclear power capacity is very cheap, and France will and should install facilities to make hydrogen when this power is not wanted by its neighbors. This hydrogen energy is cheaper than crude oil. Phénix type high temperature reactors might make very cheap hydrogen with a thermochemical process; Nuclear heat is very very cheap. Hydrogen made directly from water and coal is also cheap; sometimes cheaper than natural gas; Sequestation of CO2 is also possible where such facilities are built.

The direct oxidation of methane to methanol with oxygen from air would lower the world production CO2 by eliminating natural gas flaring. The inventers of a simple processes to do this should get a Nobel prize for chemistry and somebody, not likely the inventors, will get very rich off the process. ..HG..


Natural gas been flared should be converted to liquid fuels. It is just plain wasteful to burn it off, but that is what happens when fuel is cheap...why bother.


Nuclear hydrogen will never cut it as solution to the energy problem. There isn't enough world supply of uranium to last more than about 80 years. Solar thermal plants which generate electicity via a steam turbine is more viable. The electricity can be used to produce the hydrogen with an electrolyser.


Someone post a link to this alleged French advance in nuclear (thermochemical?) hydrogen production; it sounds too good to be true.

I recall a recent advance in methane oxidation to methanol using sulfur trioxide as the oxygen donor; the resulting SO2 is regenerated to SO3 in an external step.  If this could be done on a small enough scale or built into a floating plant for offshore use, the elimination of gas flaring by conversion to methanol would be an enormous advance.


The planet is blessed with a fusion reactor located 93 million miles away. The solar energy incident on the planet is on the order of 166 PW, 30% of it is reflected back into space and 19% is absorbed by clouds. This leaves 85 PW which can be exploited. The present world energy consumption is about 15 TW. The 85 PW then is 5000 times more than the present world consumption.

Only 8% of the land area of all the hot desert regions of the world is sufficient to generate all the energy we need using low tech trough collectors hooked up to steam turbo generators.

The sun's energy is free, it will sustain us for at least 500 million years before the sun turns into a red giant. Let's use its energy while we can.


The ability to use energy to convert CO2 to liquid fuel, more efficiently, is fine - we don't need to rely on electricity or hydrogen.

But our shortage is the energy.

richard schumacher

Do we really want to build half a million square miles of Solar collectors on Earth's surface, plus a million miles of transmission lines to connect them all to their customers?

There is thousands of times more thorium in the world than uranium. Primary nuclear fuel problem, solved.


It has been estimated that a 100 mile by 100 mile area in the Nevada desert could power all of America, so I am not seeing the half a million square miles.

Sun shines everywhere, so you do not need vast long transmission lines. What we do need is renewable methane combined cycle power plants and geothermal for base load and solar and wind to handle some of the peak loads, combined with more efficient energy usage.

Stan Peterson


It is quite apparent that you have little scientific training. While true that we have a Fusion reactor some 8 light minutes away, the energy available while prodigious, is not very concentrated, or usable. Please study the Laws of Thermodynamics and the difference between energy and enthalpy.

You are off by at least one order of magnitude if not three on the low side in estimating conventional uranium fuels. That is without even considering mining the Oceans, or reprocessing and 'actinide burning' spent fuel as all the world except the USA does. This provides as much as 90% more fuel. And it also eliminates more than half of the less than 1% of waste that remains radioactive for millenia. Meanwhile it reduces the volume of other high-level waste by some 90-95%. The Caterite idiocy, at last, is close to being reversed, by the Obama Administration and Dr. Chu.

But even if correct, you have twice as much fuel as we will need, as Fusion is less than half that time away from full commercialization. ITER, now building in Cadarache France, is both the last physics Fusion experiment, and the first pre-prototype of a commercial Fusion power plant. When operational in half a decade, it will routinely generate half a Gigawatt of Fusion energy, which is more than equal to the all the windmills operating in the USA.

Roger Pham

Nuclear fission is very powerful and concentrated, and it is this very nature that we should fear nuclear energy. I'm not alone in this fear! Remember the war on WMD? In which the US and Allies spent almost a trillion USD to find and to remove the threat of nuclear weapon in Iraq? Just imagine how much solar and wind energy capacity can be purchased for a trillion USD? Remember that sanctions against Iran and N. Korea are still in effect...and ships in and out of N. Korea are being monitored for radioactivity?

At under 1% efficiency, photosynthesis utilizing solar energy supports all life forms on earth. Petroleum, NG and Coal all came from solar energy in the past, produced at well under 1% efficiency.

We now have PV panels capable of 15% efficiency solar to electricity, up to 30-40% efficiency for concentrated PV panels. Just imagine the fantastic jump in efficiency at gathering solar energy as compared to natural photosynthesis. The surface areas needed to collect the solar energy will be far less. A PV panel on every south-facing roof, and only on existing houses and buildings, is all that will be needed to supply us with all the electricity that we will need. This can be confirmed mathematically. Excess solar energy can now be turned into fuels, such as H2, methane, and methanol, etc for use in "rainy days" or winters...


Stan Peterson,

According to the World Nuclear Association ( at the current rate of consumption with conventional reactors there are only 80 years of world uranium resources available at reasonable recovery cost levels. Nuclear power presently only supplies 5.7% of the world's total energy, thus if we hypothetically supplied the whole world with nuclear power there would be only 5 years supply.

Today there are a total of 9 Solar Energy Systems (SEGS) farms in California. 2 are located at Dagett, 5 at Kramer Junction, and 2 at Harper Lake all in the Mojave Desert. The total area occupied is 2.4 sq km generating 354 MW of power. These figures scale up to an area of 320km by 320 km if one was to supply 15 TW of energy the world uses with this technique. The 9 plants have been gradually installed from 1984 to 1990 demonstrating over 20 years of performance without malfunction. Source: Power Corp.

This installation in California serves as an existence theorem for low tech. Solar, if you will.

It demonstrates that there is sufficient area available in central Australia, for example, to generate all the power the world currently uses without the nuclear waste and safety concerns. Clearly SEGS farms would not be built in just one desert location but be spread out to suitable parts of the globe near the energy users.

Germany for example is planning to build an SEGS farm located in Algeria with power to be transmitted by high voltage DC lines to Aachen Germany.

Here is what Sir Chris Llewellyn-Smith chair of ITER council has said about low tech solar.

"The potential of solar energy is so great that developing means to tap it more efficiently and store it must be a priority."

The consolidated utility time (CUT) of various energy sources has been estimated by a number of researchers. CUT is the time it would take for each resource to run down reasonably recoverable reserves if it individually had to supply the whole world's energy needs, in isolation.

The CUT for Solar Hydrogen is 1 billion years.
Nuclear Fusion: 100 years.
Coal:35 years.
Gas: 14 years.
Oil: 14 years.
Nuclear Fission: 5 years.

For long term sustainability we should put our money on the Solar Hydrogen economy. It may be low tech but has none of the pollution, green house gas, waste storage, or safety issues.

The only issue for hydrogen is that the hydrogen leakage be less than 5% otherwise we would be out of water in a billion years. You see if hydrogen is lost it eventually makes its way into the stratosphere where a fraction of it will end up in outer space. But since planet earth will be un inhabitable by that time frame anyway it's really not a problem.

Finally, hydroelectricity currently provides 20% of the world's energy. In case you didn't know, Stan, the ultimate source of hydroelectric power is solar energy (via rain). This is a salient reminder that large power levels can be obtained compared to nuclear power if one taps the sun directly even though as some critics charge, yourself included, that solar energy is much too diffuse to be practical.

You're wrong on one other point, I do have an advanced engineering degree. I'm familiar with the laws of thermodynamics, entropy and all the rest, hold 14 patents in electronics etc., but then I digress.


Stan Peterson

You propose mining the oceans for unranium.

Let's see now, there are approximately 4.5 billion tonnes of uranium in the seas. That's a lot of uranium you would say.

The down side however is that the uranium concentration is 3 parts per billion!

Research on this was abandoned in the 1960s due to poor recovery efficiencies. Hydrated titanium oxide was used as the absorbent but was found to be imprcatical.

For a review of the difficulties I suggest you refer to: A. D. Klemers and H. E. Goeller, "Uranium Recovery From Low-Level Aqueous Sources", Oak Ridge National Labs, Tech. Report ORNL/TM-7652, 1981.

More recently special polymer fiber membranes or chelating resins with various chemicals are being researched for absorbing uranium from sea water. As well as questionable costs , practicalities, and recovery rates it is unlikely that these materials would be sustainable for the sheer volumes of water that would need to be sifted.

It is also unknown if uranium removal would be detrimental to aquaculture where there is a possibility that marine life DNA mutation rates would drop off and impact the long term survival adaptability.


Stan Petersen

Fusion has been promised to be ready in the early 1970s for commercial power generation in 20 years this is still the case today.

Fusion reactors use tritium for their operation. Tritium is produced on earth by reactin neutrons with lithium. tritium is sufficiently dangerous that nuclear authorities limit its absorption by the walls of the reactor. Therein lies the problem with fusion.

Estimates of commercial fusion reactors by 2050 are simply over optimistic. The ITER has the largest ever approved tritium retention limit of 350 g. to put this into context, with carbon walls ITER would reach this limit in about 1 week of operation. The reactor would then have to be powered down to allow access to clean the walls for the removal of tritium before fusion operation can be resumed. Exactly how to clean the walls, how to manage the resulting toxic dust, and the magnitude of the resulting down time are all uncertainties without any current solutions. The problems of neutron embrittlement still are not solved.

Furthermore, the super conducting magnets to convine the plasma use niobium alloys. To attain 15TW would exhaust world niobium reserves, assuming 500 tonnes of niobium per 1 GW fusion reactor. Niobium is also used for superalloys in engines. Thus a full analysis of the materials inventory for fusion reactors is still required.


Mannstein, you are using bogus figures.  The technology appraisal assumes LWRs, but at the uranium prices implied by scarcity FBRs will be economical.  FBRs not only turn 95% of the spent nuclear fuel in the world into actual fuel (actinides and remaining uranium), it also turns all the depleted uranium into fuel and reduces the per-kWh cost of U recovered from seawater by a factor of 100.

BOTE:  the USA has roughly 50,000 tons of SNF in inventory.  At 0.8 tons/GW-yr in a Gen IV fast-spectrum reactor, this would supply the non-renewable electrical demand of the US grid for about 170 years.  The DU inventory is perhaps 4 times that much, and then we have both uranium and thorium available to mine.



The numbers I'm quoting are sourced at Check out the following link:

There are only 80 years supply of "recoverable" uranium to supply the present reactors which provide 5.7% of the world's total electricity, that is 15 TW. If present reactors were to generate the full amount to reduce GHG to near zero the supply would last only 5 years.

The uranium in seawater is not "recoverable" with present day technology. It's in the water alright but to extract it is not economic hence not "recoverable".

The FBRs fans claim to extend the useful lifetime of uranium by a factor of 60. However, since the first US breeder in 1951, they have not met with commercial success. Thus FBRs turn out not to be cost competitive as well as having a number of safety issues.

I refer you to the report by M. V. Ramana and J. Y. Suchitra, "Slow and stunted:Plutonium accounting and the growth of fast breeder reactors in India" Energy Policy, vol. 37, no. 12, pp.5028-5036, 2009.

The reactors use liquid sodium as a coolant and there have ben safety problems with leakage. The US Clinch River Breeder Reactor construction was abandoned in 1982. After a serious leak and fire during 1995, the reopening of Japan's Monju reactor has been stalled. France's Superphenix reactor closed down in 1997 due to it's rate of mafunction and sodium leaks. During its 11 year lifetime there were 2 years of accumulated downtime due to technical faults at a total cost of 12 billion dollars US. Ther are many uncertainties with FBRs: their life cycle efficiencies are unknown and how does one therefore compare their energy return on investment (EROI) with other energy generation methods?

Thorium is claime to be the answer when uranium stocks run outas it is a more "abundant" element. However, its occurence is only 3 times that of uranium, which is not significant. Moreover the economically "recoverable" world reserves of thorium are only half the reserves of uranium.

Roger Pham

Thanks, Mannstein, for educating us on the problems with the much-touted FBR!


Mannstein, you did it again.  SEVERAL times:

There are only 80 years supply of "recoverable" uranium[1] to supply the present reactors[2] which provide 5.7% of the world's total electricity[3], that is 15 TW[4]. If present reactors[5] were to generate the full amount to reduce GHG to near zero the supply would last only 5 years.
Let's go over this point by point.
  1. "Recoverable" depends on price.  The supply available at $200/lb is a large fraction of the amount in the oceans, and that is with current technology.
  2. "Present reactors" (LWRs, not FBRs) are only used because uranium is cheap.  The supply of LEU is 1/6 or less of the supply of NU, and perhaps 5% of LEU is fissioned in an LWR; this is a total utilization of less than 1%.  FBRs can use close to 100% of NU.
  3. US reactors ALONE supply about 5% of the world's electricity; the world total is about 15%.
  4. You're talking electricity but comparing it to raw (thermal) world energy consumption from all supplies (about 13 TW).  In other words, you are counting it as if humanity would take nuclear electricity and throw it into resistance heaters to make steam to run today's coal-fired powerplants.
  5. See #2.
World electric consumption in 2004 is estimated to be as high as 17,400 TWh, or about 2 TWe continuous.  Double that to allow electrification of all ground transport and industrial process heat, and we're up to 4 TWe continuous.  At 0.8 tons of uranium or thorium per GWe/yr in an FBR or LFTR, 4 TWe (or the thermal equivalent) would require 3200 tons of uranium or thorium per year.  The estimated 5.5 million tons of easily recoverable uranium would last about 1500 years at this rate.

Now stop using misleading and incommensurable figures to lie.

Tim Duncan

Nice going Poet,I think you got the last word. I enjoyed your apparent mastery of the subject. Why don't we use FBR's? What do the French use?

Henry Gibson

The French are using their surplus nuclear generated electricity to generate hydrogen by plain electrolysis. This is mentioned on the website of the French power company. Small electrolysis units could be situated anywhere hydrogen is being used for chemical production or could be used if available. Hydrogen can be used to support some kinds of fermentation including perhaps ethanol production. An "ANTI-FUEL-CELL" that produces methanol from electricity and CO2 and water is what could be used now. Hydrogen produced from cheap industrial off peak French nuclear electricity is far cheaper fuel than crude oil at $150. Most of the cost of the hydrogen is the capital cost of the electrical equipment and not the cost of the uranium. The use of accelerator driven reactors, proposed by Nobel prise winner Prof. Carlo Rubia, make it possible to use all thorium, all uranium and depleted uranium and used fuel rods and any elements heavier than uranium now produced in reactors including all isotopes of plutonium. All of these materials can be used as fuel in Rubbia reactors. The accelearators need for these reactors are already working in prototype form and used for neutron studies. Just look up the new neutron producton facility at ORNL.

A combination of fusion reactors with fission reactors can also increase the fuel supply in the same way. Fusion reactors, if ever built, can increase the ability to produce plutonium for bombs by a large factor because they are an infinite source of neutrons.

It is even thermodynamically possible to build an energy releasing reactor that fissions lead, gold, mercury and a few dozen other elements. Such reactors may be easier to build and operate than fusion reactors. ..HG..

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