We assume, given the description of the problem in the OP, that the rectangle is a horizontal strip of height $2$ and width $n$.
Proof by Contradiction. Suppose we had a covering of the $2 \times n$ rectangle containing an odd number of horizontal dominoes. Then either the upper row or the lower row contains more dominoes than the other; without loss of generality, assume the upper row contains more. Then the upper-row horizontal dominoes cover more squares than the lower-row ones do. But vertical dominoes must cover an equal number of upper and lower dominoes. So more upper-row squares are covered than lower-row squares, violating the definition of the rectangle. Ergo, no such covering is possible.
Proof by Induction. As you point out the number of horizontal dominoes is clearly zero (and therefore even) for $n = 0$ or $1$. For $n \geq 2$, consider the last two squares on the right. There are two cases: In one case, they are covered by a single vertical domino, in which case the number of horizontal dominoes is equal to the number in the first $2 \times n-1$. In the other case, they are covered by two horizontal dominoes, in which case the number of horizontal dominoes is two more than the number in the first $2 \times n-2$. In either case, the parity of the number of horizontal dominoes is unaffected, so the result obtains.
You've added a second question: how to show that the number of ways to cover the $2$-by-$n$ rectangle with $2j$ horizontal dominoes (and therefore $n-j$ vertical ones).
The easiest way I can think of to proceed is to observe that each row must look identical. Vertical dominoes perforce look identical in each row, and if the horizontal ones don't line up one on top of the other, then there will be an extra space left over somewhere. (Actually, two extra spaces, but at any rate—extra spaces.)
Therefore, we can just count the number of ways that we can cover a single strip of $n$ squares with pieces of either one square (those represent half a vertical domino) or two squares (those represent a horizontal domino with a matching domino in the other row). If there are $j$ two-square pieces altogether in the strip, then there must be $n-j$ pieces in the row, because the two-square pieces collectively cover $2j$ squares, leaving the remaining $n-2j$ squares to be covered by $n-2j$ one-square pieces: $n-2j+j = n-j$ pieces in all.
Each arrangement corresponds to choosing $j$ of those $n-j$ pieces to be the two-square pieces, so the number of ways of doing that is
$$
\binom{n-j}{j}
$$
I'm assuming you can handle the rest of the deduction.