Let $\mathfrak g$ be a finite dimensional nilpotent Lie Algebra over a field $F$ (is characteristic zero necessary?). Why is the map $ad: \mathfrak g \to Der (\mathfrak g), x \mapsto {ad}_x$ not surjective?
One result, which is simple to show, is that there is an ideal $I$ of codimension 1 in $\frak g$ and an element $x \not\in I$ so that $x\not\in[\mathfrak g, \mathfrak g]$. So my idea is to build a derivation that has $x$ in its image, since $x$ will not be in the image of any adjoint. But here is where I am getting stuck (unless this is entirely the wrong approach).
For a nilpotent Lie algebra there exists always an outer derivation, i.e., a derivation which is not of the form $ad(x)$ for some $x$. This result of Dixmier shows that the map there cannot be surjective for nilpotent Lie algebras.
As to why this is so- see the proof of Dixmier in the paper
Dixmier, J., Cohomologie des alg`ebres de Lie nilpotentes, Acta Sci. Math. Szeged 16(1955),246–250.