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The smog test wouldn't start unless he's within the range (I don't recall exactly but it might be +/- 1 MPH) for that particular test, so why would he run the 25 MPH test at 15 MPH? The machine would just wait and wait, and if the alotted time passed, it would skip to the next test, resulting in an automatic FAIL for that test it skipped. But no, simply changing the ECU isn't going to change your emissions. High NOX means your combustion chamber is higher than normal. That could be a result of many things -- malfunctioning EGR, too much gunk in your engine, bad cooling system, etc.
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