In this paper, we provide the spectral decomposition in Hilbert space of the $\mathcal{C}_0$-semigroup $P$ and its adjoint $\hatP$ having as generator, respectively, the Caputo and the right-sided Riemann-Liouville fractional derivatives of index $1<α<2$. These linear operators, which are non-local and non-self-adjoint, appear in many recent studies in applied mathematics and also arise as the infinitesimal generators of some substantial processes such as the reflected spectrally negative $α$-stable process. Our approach relies on intertwining relations that we establish between these semigroups and the semigroup of a Bessel type process whose generator is a self-adjoint second order differential operator. In particular, from this commutation relation, we characterize the positive real axis as the continuous point spectrum of $P$ and provide a power series representation of the corresponding eigenfunctions. We also identify the positive real axis as the residual spectrum of the adjoint operator $\hatP$ and elucidates its role in the spectral decomposition of these operators. By resorting to the concept of continuous frames, we proceed by investigating the domain of the spectral operators and derive two representations for the heat kernels of these semigroups. As a by-product, we also obtain regularity properties for these latter and also for the solution of the associated Cauchy problem.