Proof that the rise is not due to man? No.
Reasonable doubt? You bet.
The first one, from 1996, dates back to the heyday of Usenet, and contains an itemized list of various types of evidence. I have used some of these points in different FR discussions.
Why does atmospheric CO2 rise ?
How do we know that recent CO2 increases are due to human activities?
How Do We Know that the Atmospheric Build-up of Greenhouse Gases Is Due to Human Activity?
Ice Bubbles Reveal Biggest Rise in CO2 for 800,000 Years
Reasonable doubt? You bet.
Maybe O.J. didn't murder Nicole and Ronald Goldman, either.