Vanadium Phosphate Catalyst

Methane, CH₄, in natural gas can be used as a raw material to produce bromomethane, CH₃Br. Bromomethane (methyl bromide) can then be used in the chemical industry to produce fuels, chemicals, polymers and pharmaceuticals. When  bromomethane is converted into fuels and other chemicals, bromine is released in the form of hydrogen bromide, HBr. Using oxygen and a suitable catalyst, bromine from the hydrogen bromide by-product is embedded back into bromomethane so that no bromine is lost from the system.
Researchers at ETH, Zurich, have identified vanadium phosphate as an ideal catalyst for this reaction.
Vanadium(III) phosphate (vanadium(3+) phosphate), has the structure shown below:

It is a relatively mild oxidising catalyst.
It is a strong enough oxidising catalyst to allow hydrogen bromide to react with oxygen at the surface of the catalyst, but, it is not strong enough to oxidise the methane and brominated reaction products.
It is therefore possible to brominate methane in a single step at atmospheric pressure and at a temperature below 500°C.  The catalyst is also stable, able to resist the corrosive reaction environment.
This makes it an attractive catalyst for this important, industrial, chemical reaction.

Reference:
Vladimir Paunović, Guido Zichittella, Maximilian Moser, Amol P. Amrute, Javier Pérez-Ramírez. Catalyst design for natural-gas upgrading through oxybromination chemistry. Nature Chemistry, 2016; DOI:10.1038/nchem.2522

Further Reading:
Lewis Structures (electron dot diagrams): http://www.ausetute.com.au/lewisstr.html
2-Dimensional Structural Formula: http://www.ausetute.com.au/structural2D.html
Molecular Formula: http://www.ausetute.com.au/molecularformula.html
Halogenation of Hydrocarbons: http://www.ausetute.com.au/halogalk.html
Energy Profiles: http://www.ausetute.com.au/enerprof.html
Reaction Rates: http://www.ausetute.com.au/reactrate.html
Redox Reaction Concepts: http://www.ausetute.com.au/redoxreactions.html

Suggested Study Questions:

1. Draw the Lewis Structures (electron dot diagrams) for each of the following molecules:
   • methane
   • bromomethane
   • hydrogen bromide
2. Draw the 2-dimensional structural formula for each of the following molecules:
   • methane
   • bromomethane
   • hydrogen bromide
3. Give the molecular formula for each of the following molecules:
   • methane
   • bromomethane
   • hydrogen bromide
4. Write a chemical equation to represent the reaction between methane and bromine to produce bromomethane
5. Name the type of reaction given in question 4.
6. Give the reaction conditions necessary for this reaction in question 5 to occur at room temperature and pressure in your laboratory.
7. Why do you think a catalyst is required for this reaction above in order to produce commercial quantities of bromomethane?
8. Which organic compound, methane or bromomethane, do you expect to be the most chemically reactive? Explain your answer.
9. What is meant by the term "oxidising agent"?
10. Is the bromination of methane using bromine a redox reaction? Explain your answer.
11. Refer to the structure of vanadium(III) phosphate given in the article. Give the oxidation state (oxidation number) for each of the following:
    • vanadium
    • oxygen
    • phosphorus
12. Why do you think vanadium phosphate is talked about as being an "oxidising catalyst" rather than as an "oxidising agent"? Explain your answer.

Hard Metal

Hard metal is a mixture of a hard carbide phase, tungsten carbide, and a tougher metal phase, cobalt. It is produced by sintering, a process in which fine powders of tungsten carbide and cobalt are heated up so that the cobalt melts and the material is pulled together by capillary force. This results in a solid material consisting of hard tungsten carbide grains surrounded by the tougher cobalt-rich cement phase.

The size of the tungsten carbide grains determines the hardness of the hard metal.
Scientists know that by doping the material, that is, by adding another substance in tiny amounts, they can limit the size of the grains. For example, adding a tiny amount of vanadium can limit the growth of the grains, instead of growing grains 1/1000 mm in diameter, the addition of vanadium results in grain sizes about 1/10,000 mm. Scientists at the Chalmers University of Technology in Sweden have just used high-resolution electron microscopy to observe an extremely thin layer, only 2 atom layers thick, of a cubical structure on the tungsten carbide grains which they believe is affecting the growth of the grains.

Reference:
Expertanswer (2010, June 14). Materials researchers micromanage atoms in hard metal. ScienceDaily. Retrieved June 16, 2010, from http://www.sciencedaily.com­ /releases/2010/06/100614093343.htm

Study Questions:

1. Write the symbol for each of the following elements: tungsten, carbon, cobalt, vanadium.
2. To which group of the Periodic Table do tungsten, cobalt and vanadium belong?
3. Give possible oxidation states (numbers) for tungsten, cobalt, vanadium and carbon.
   
4. Suggest a formula for tungsten carbide.
5. Would you expect larger or smaller grains of tungsten carbide to grow at higher temperatures?