Determine all elements of group $\operatorname{Hom}(S_{3}, \mathbb{Z}_{2})$.
I was thinking of mapping generators of group $D_{3}$ (which is isomorphic to the group $S_{3})$ to elements of group $\mathbb{Z}_{2}$. So, if $r,f$ are generators of $D_{3}$, respecting the the rule that homomorphism maps neutral element to neutral element, I believe that there are $2$ homomorphisms, $$f_{1} (r) = f_{1}(f) = 0 $$ and $$f_{2} (r) = 0,\quad f_{2}(f) = 1.$$ Is that good thinking?
In the dihedral group $D_3$ (or $D_6$ depending on notation) you have the relations $r^3=f^2=rfrf=e$ (and those relations generate all relations). Hence, if you define a map to another group $G$ $$ \varphi: D_3 \rightarrow G, \ \varphi(r)=g, \ \varphi(f)=h $$ then this will define a group homomorphism iff (now I use multiplicative notation for the group $G$) $$ g^3=\varphi(r)^3 = e_G, \ h^2=\varphi(f)^2 = e_G, \ ghgh=\varphi(r) \varphi(f) \varphi(r) \varphi(f)= e_G.$$ In our case, this means (now in additive notation) in $\mathbb{Z}/2\mathbb{Z}$ $$ 3g = 0, \ 2h =0, 2g + 2h =0 $$ This implies $g=3g=0$ and the remaining equations are satisfied no matter what the choice of $g,h\in \mathbb{Z}/2\mathbb{Z}$. Hence, we get exactly the two choices you wrote.