Question 1
I create a triangle by choosing three vertices from the seven given.
The only time I get a degenerate triangle is when the three vertices are in a straight line which happens in three cases - $\{A,O,D\}, \{B,O,E\}, \{C,O,F\}$.
Subtracting these cases I get $$\binom{7}{3} - 3 = 32$$
Question 2
I think there are five essentially different triangles all obtained by rotation or inversion of the following triangles $$ AOB, AFB, AEB, AOC, AEC $$ and the number of times each of these triangles appears is as follows $$6,6,12,6,2 $$ which adds up to $32$, as desired.
Jean Hominal makes an important point in the comments
Triangles $AFB$ and $AOC$ are congruent so could be obtained one from the other by an extra translation although we'd lose the overall symmetry of the hexagon. My answer above assumes that we can rotate and invert while maintaining the hexagonal symmetry but if you would like to consider congruent triangles as being the same then the answer would be four.