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Generally speaking, there's nothing to prevent you from generating additional income from any source. However, there are various exceptions.
For example, if is the case that you would be operating in competition with your existing employer, then clearly ther would be a conflict of interest that your employers couldn't be reasonably expected to accomodate.
Alternatively, they might require some sort of assurance that your additional activities weren't impacting on your ability to perform effectively for them (e.g. as a result of tiredness, fatigue, etc.).
In terms of any additional income you generate, this would need to declared to the Revenue Comm who would decide on the extent to which it would generate a tax liability. If you were charging VAT, you would need to registered to do so.