Prophet Mohammad did that maybe 1500 years ago. Can't think of anyone who did that before him (peace be upon him)
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The first written account of freeing of slaves is Moses leading the Israelites out of slavery, so I guess you could say they were the first free slaves.
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The slaves used either the underground railroad, or they found a crafty way to act like a free person.
The state that did not free the slaves was Delaware. Kentucky, Maryland, and Missouri did not free slaves either.
Abraham Lincoln wanted to free the slaves.