Let $f$ be a smooth function, then
$$df = \sum_{j=1}^n\frac{\partial f}{\partial x^j}dx^j$$
and
\begin{align*}
d^2f = d(df) &= \sum_{i=1}^n\sum_{j=1}^n\frac{\partial^2f}{\partial x^i\partial x^j}dx^i\wedge dx^j\\
&= \sum_{i<j}\frac{\partial^2f}{\partial x^i\partial x^j}dx^i\wedge dx^j + \sum_{j<i}\frac{\partial^2f}{\partial x^i\partial x^j}dx^i\wedge dx^j\\
&= \sum_{i<j}\frac{\partial^2f}{\partial x^i\partial x^j}dx^i\wedge dx^j - \sum_{j<i}\frac{\partial^2f}{\partial x^i\partial x^j}dx^j\wedge dx^i\\
&= \sum_{i<j}\frac{\partial^2f}{\partial x^i\partial x^j}dx^i\wedge dx^j - \sum_{i<j}\frac{\partial^2f}{\partial x^j\partial x^i}dx^i\wedge dx^j\\
&= \sum_{i<j}2\left(\frac{\partial^2f}{\partial x^i\partial x^j} - \frac{\partial^2f}{\partial x^j\partial x^i}\right)dx^i\wedge dx^j.
\end{align*}
The fact that $d^2 = 0$ follows from the fact that partial derivatives commute for a smooth function, i.e.
$$\frac{\partial^2f}{\partial x^i\partial x^j} = \frac{\partial^2f}{\partial x^j\partial x^i}.$$