Rectenna is the key component in radio-frequency circuits for receiving and converting electromagnetic waves into direct current. However, it is very challenging for the conventional semiconductor diode switches to rectify high-frequency signals for 6G telecommunication (>100 GHz), medical detection (>THz), and rectenna solar cells (optical frequencies). Such a major challenge can be resolved by replacing the conventional semiconductor diodes with tunneling diodes as the rectenna switches. In this work, metal–insulator–metal (MIM) tunneling diodes based on 2D insulating materials were designed, and their performance was evaluated using a comprehensive simulation approach which includes a density-function theory simulation of 2D insulator materials, the modeling of the electrical characteristics of tunneling diodes, and circuit simulation for rectifiers. It is found that novel 2D insulators such as monolayer TiO2 can be obtained by oxidizing sulfur-metal layered materials. The MIM diodes based on such insulators exhibit fast tunneling and excellent current rectifying properties. Such tunneling diodes effectively convert the received high-frequency electromagnetic waves into direct current.