For Q1, the answer is yes if we consider image-finite systems: for all node $t$ and label $a$, the number of $a$-successors of $t$ must be finite. In this case you don't even need fixpoints of the $\mu$-calculus, only the fragment called Hennessy-Milner Logic to distinguish non-bisimilar structures [HM85]. This is known as the Hennessy-Milner Theorem. Intuitively, the non-bisimilarity can be seen in a finite amount of steps of the form "there exists an $a$-successor", or "for all $a$-successor".
For more general cases, the paper [FCM17] might be of interest, in particular it gives at the end an example of two non image-finite structures (actually two nodes in the same structure) which are not bisimilar, but cannot be distinguished with HML formulas. I suspect this is still true for $\mu$-calculus formulas, but to be verified.
As for Q2, I'm not sure there is a clear "maximal class". A class $\mathcal C$ with your conditions must at least satisfy the following requirements:
- at most one element per bisimulation equivalence class
- $\mathcal C$ is countable
But then you have some room, since starting from such a class you can always replace one element by another which is bisimilar to it.
It is not even true that $\mathcal C$ must only contain finitely describable elements, since you can always take $\mathcal C=\{T\}$, where $T$ is any structure, and complete it to a maximal class, and it would satisfy the requirements (although artificially). You probably have other conditions in mind for such a class, that would rule out the above example.
A natural such class is the set of regular ranked binary trees (where successors are ordered). Here "regular" means that the number of distincts subtrees is finite, even though the tree can be infinite.
[HM85] Matthew Hennessy & Robin Milner (1985): Algebraic laws for nondeterminism and concurrency. Journal of the ACM, doi:10.1145/2455.2460.
[FCM17] Ferlez, J., Cleaveland, R. and Marcus, S., 2017. Bisimulation and Hennessy-Milner Logic for Generalized Synchronization Trees. arXiv preprint arXiv:1709.00827.