Not to mention you have to observe the laws of conservation of energy. I guess, if you captured the light coming out of the LED as well as the heat, and had a 100% converstion efficiency...but at the same time, you would not be able to observe the light being emitted, or use it for any practical purpose, or even measure it. So, on a different note, you could build a "black box" with an LED, thermocouple, and photocell inside and call it a perpetual motion machine, claiming that opening the box or measuring the LED's output will cause it to cease to function...well knowing, in fact, that it never stays lit at all. /ubbthreads/images/graemlins/grin.gif
On a more serious note, the thermocouple relies on a delta of heat to generate the electrical curent, much like a water turbine relies on a pressure differential...given that the higher operating temperature of the LED would cause it to get dimmer, you may be losing ground instead of gaining it. /ubbthreads/images/graemlins/icon23.gif Conversely, the LED's efficiency gets better with a decrease in temperature. I think it's either the blue or cyan Luxeon that has a sharp rise in output as ambient gets colder, whereas the other types have a more linear slope.