Humans discovered hundreds of knots just playing around, and developed excellent knots in the past 400 years; new knots, never before tied, were invented some ~100 years ago. One imagines that a bit of searching with a computer might find a few cases that were overlooked.
For example, take a look at https://en.wikipedia.org/wiki/Butterfly_loop and https://en.wikipedia.org/wiki/Butterfly_bend and https://en.wikipedia.org/wiki/Hunter%27s_bend and https://en.wikipedia.org/wiki/The_Ashley_Book_of_Knots
No. I don't believe that. The archeological record has evidence of humans making rope for tens of thousands of years. I can believe that nobody alive had seen and named those particular interlocked pairs of overhand knots; that no written record of them existed until recently. But your claim that those knots had never been tied is quite presumptuous.