Energy harvesting (EH) emerges as a novel technology to promote green energy policies. Based on Cognitive Radio (CR) paradigm, nodes are designed to operate with harvested energy from radio frequency signals. CR-EH systems state several strategies based on sensing and access policies to maximize throughput and protect primary users from interference, simultaneously. However, reported solutions do not consider to maximize detection performance to detect spectrum holes which represent a major drawback whenever available energy is not efficiently used. In this concern, this paper addresses optimal sensing policies based on energy harvesting schemes to maximize probability of detection of available spectrum. These novel policies may be incorporated to previous reported solutions to maximize performance. Optimal processing scheduling schemes are proposed for offline and online scenarios based on convex optimization theory, Dynamic Programming (DP) algorithm and heuristic solutions (Constant Power and Greedy policies). Performance of proposed policies are validated by simulations for common detection techniques such as Matched Filter (MF), Quadrature Matched Filter (QMF) and Energy Detector (ED). As a result, it is shown that the best detection scheme theoretically addressed by MF, does not always perform better than the poorest detection scheme, given by the ED, in an energy harvesting scenario.