Q2: Complexification $(-) \otimes_{\mathbb{R}} \mathbb{C}$ can be thought of very explicitly as follows: the complexified Lie algebra has exactly the same structure constants as the original Lie algebra, but you're now allowed to take complex combinations of the basis elements, not just real ones. Said another way, $\mathfrak{g}_{\mathbb{C}}$ as a vector space has a decomposition $\mathfrak{g} \oplus i \mathfrak{g}$ into real and imaginary parts, and the Lie bracket extends the Lie bracket of $\mathfrak{g}$ linearly.
Q1A: Abstractly this computation can be carried out using Galois cohomology; we get that the set of real forms of $\mathfrak{sl}_2(\mathbb{C})$ is parameterized by
$$H^1(\text{Gal}(\mathbb{C}/\mathbb{R}), \text{Aut}(\mathfrak{sl}_2(\mathbb{C})) \cong H^1(\mathbb{Z}_2, PGL_2(\mathbb{C}))$$
(it's not entirely obvious that the automorphism group is $PGL_2(\mathbb{C})$ but it follows from the fact that the Dynkin diagram of $\mathfrak{sl}_2(\mathbb{C})$ is $A_1 = \bullet$, so there are no "diagram automorphisms"), where $\mathbb{Z}_2$ acts by complex conjugation on $PGL_2(\mathbb{C})$ in the obvious way. This Galois cohomology group also classifies real forms of $M_2(\mathbb{C})$ (because it also has automorphism group $PGL_2(\mathbb{C})$) and a nontrivial such real form (other than $M_2(\mathbb{R})$) must, by standard facts about central simple algebras, be a $4$-dimensional real division algebra, hence from the Frobenius theorem must be the quaternions $\mathbb{H}$. (Over other fields we get more general quaternion algebras.)
It follows that $H^1(\mathbb{Z}_2, PGL_2(\mathbb{C}))$ has two elements, so there are two real forms, and since $\mathfrak{sl}_2(\mathbb{R})$ and $\mathfrak{su}(2)$ are two real forms (which can be distinguished e.g. by the signature of the Killing form) these are all the real forms. Alternatively, it's actually possible to write down a natural bijection between real forms of $M_2(\mathbb{C})$ and real forms of $\mathfrak{sl}_2(\mathbb{C})$: we define the trace and then pass to the Lie subalgebra of elements of trace zero. Applied to $\mathbb{H}$ this produces the Lie algebra of purely imaginary quaternions $\mathfrak{sl}_1(\mathbb{H}) \cong \mathfrak{sp}(1) \cong \mathfrak{su}(2)$.
In general real forms of simple Lie algebras are classified by Satake diagrams, which are Dynkin diagrams with some extra structure. I don't know anything about this, though.
Q1B: But that was very high-tech. It's possible to give a lower-tech and fairly direct answer. Suppose $\mathfrak{g}$ is a $3$-dimensional real Lie algebra complexifying to $\mathfrak{sl}_2(\mathbb{C})$. Then $\mathfrak{g}$ must be simple (since $\mathfrak{sl}_2(\mathbb{C})$ is simple). Consider the adjoint action $\text{ad}_X : \mathfrak{g} \to \mathfrak{g}$ of any nonzero $X \in \mathfrak{g}$. By simplicity we must have $\text{tr}(\text{ad}_X) = 0$; equivalently, the image of $\mathfrak{g}$ in $\mathfrak{gl}(\mathfrak{g})$ must have image in $\mathfrak{sl}(\mathfrak{g})$ (otherwise the trace would give a nontrivial abelian quotient). So the eigenvalues of $\text{ad}_X$ add up to $0$, and since $\text{ad}_X(X) = 0$ one of the eigenvalues is $0$, meaning that the other two eigenvalues are either two nonzero real eigenvalues $r, -r$ or two nonzero purely imaginary eigenvalues $is, -is$. We now split into cases:
Case 1: Some $H \in \mathfrak{g}$ has two nonzero real eigenvalues $r, -r$. By scaling $H$ we can assume WLOG that the eigenvalues are $2, -2$ (this isn't really necessary but it's traditional). Let $X, Y$ be the corresponding eigenvectors, so we have $[H, X] = 2X, [H, Y] = -2Y$. The Jacobi identity gives
$$[H, [X, Y]] = [[H, X], Y] + [X, [H, Y]] = 2 [X, Y] - 2 [X, Y] = 0$$
from which it follows that $[X, Y]$ must be a multiple $cH$ of $H$. By rescaling $X$ we can assume WLOG that $[X, Y] = H$, and now we've written down the traditional presentation
$$[H, X] = 2X, [H, Y] = 2Y, [X, Y] = H$$
of $\mathfrak{sl}_2(\mathbb{R})$ (and in fact of $\mathfrak{sl}_2(F)$ for any field $F$; the $2$s matter in characteristic $2$). So $\mathfrak{g} \cong \mathfrak{sl}_2(\mathbb{R})$ in this case.
Case 2: Every $X \in \mathfrak{g}$ has purely imaginary eigenvalues. By scaling appropriately we can find $X \in \mathfrak{g}$ with eigenvalues $i, -i$. In the complexification $\mathfrak{g}_{\mathbb{C}}$ let $Z + iY, Z - iY$ be the corresponding two eigenvectors (it's a general fact that the eigenvectors must be complex conjugates), where $Z, Y\in \mathfrak{g}$: this gives
$$[X, Z \pm iY] = [X, Z] \pm i [X, Y] = -Y \pm iZ$$
hence $[X, Z] = -Y$ and $[X, Y] = Z$; rearranging the first one gives $[Z, X] = Y$. The Jacobi identity gives
$$[X, [Y, Z]] = [[X, Y], Z] + [Y, [X, Z]] = 0$$
so $[Y, Z]$ must be a scalar multiple $cX$ of $X$. By rescaling both $Y$ and $Z$ by $\sqrt{|c|}$ (we can't just rescale one of them this time) we can assume WLOG that $c = \pm 1$. If $c = -1$ we get $[Y, X] = -Z, [Y, Z] = -X$ so $Y$ has eigenvectors $X \pm Z$ with real eigenvalues $\mp 1$ which contradicts our assumption that every element has imaginary eigenvalues. So $c = 1$, and now we've written down the traditional presentation
$$[X, Y] = Z, [Y, Z] = X, [Z, X] = Y$$
of $\mathfrak{su}(2)$ (more or less).
This argument does not use the full strength of the assumption that $\mathfrak{g}$ is a real form of $\mathfrak{sl}_2(\mathbb{C})$: actually all it uses is that $\mathfrak{g}$ is perfect (has trivial abelianization). So this is a classification of $3$-dimensional perfect real Lie algebras (perfect is equivalent to simple in dimension $3$), which fits into the Bianchi classification of all $3$-dimensional real Lie algebras.
Edit, 9/27/22: A recent question has shown me that there's a small gap in this argument; the possibility that $\text{ad}_X$ is nilpotent for every $X \in \mathfrak{g}$ (so that $\text{ad}_X$ never has distinct eigenvalues) needs to be ruled out. This can be done following the argument here from Fulton and Harris although maybe simpler arguments are possible.