Porcelain and ceramic tiles are non-combustible and handle heat well, so they're widely used around wood burners and as hearths. Make sure you use a heat-resistant adhesive and grout.
Hearth size and distances are set by Building Regulations and your stove manufacturer's instructions, so please check these with your stove installer before ordering. Your installer should be registered with HETAS (the Heating Equipment Testing and Approval Scheme), the official UK scheme for wood-burning and solid fuel stove installers.