Moles - an isolation framework for Microsoft .NET
Moq is a strongly typed and minimalistic mocking framework for .NET.
Personally i think moles is much better suited for mocking the unmockable and i prefer a combination of moq for my own interfaces and classes and moq for framework and externalities like file i o gui db connections etc
Interaction testing using moles
In other words moq is not going to be any help to you here;for mocking statics i use a tool called moles which is free
How to mock ConfigurationManager.AppSettings with moq