The largest entry of a positive semidefinite matrix $A$ always lies on the diagonal, but that doesn't mean every diagonal entry of $A$ is the largest element among its row/column. E.g. $$A=\pmatrix{5&2\\ 2&1}$$ is positive semidefinite, but $1$ is not the largest entry on the its row/column.
However, if $A$ is both positive semidefinite and doubly stochastic, is it true that each diagonal element is the largest entry on its respective row?