Ex-boxer here:
Knuckle toughening is bullshit. The best thing you can do to protect your knuckles is to improve your grip. THe tighter your grip when you throw a punch, the less room there is for the vibrations at impact which are what cause the real damage.
The theory behind knuckle toughening and other bone toughening exercises is that repeated impacts or pressure will cause the bone to grow denser , and therefore stronger over time. This is a bad, bad misconception. It is true that if you severely abuse a bone, it becomes denser as it repairs itself, but this actually makes it weaker.
What happens is that the impacts slowly collapse the honeycomb structure of the bone tissue which then builds new tissue to repair itself, becoming denser. It’s heavier, and seems stronger. The impacts don’t hurt as much. You stop getting bone bruises and think you’re pretty tough.
What you’ve just done though is cut all the safety margin out of your bone tissue, all the real strength and resilience, and you’re much likelier to have a catastrophic injury, i.e. shatter the bone.
In boxing, it’s called “glass hands.” An idiot who works out on the bags without protection for a couple of years will get them.
Also if you have an accident in the ring and break your hand, you have to be very careful when you try to come back , or you’ll get them. The calcification makes them brittle, and they’ll often break repeatedly, though rarely in the same place.
You can build up a horny ridge of skin over your knuckles which will give them some protection, and you can strengthen the muscles and tissue that surround and encase your bones, but they are never so strong as before you start to abuse them.
I read about this probably ten years ago in a boxing magazine, discussing the results of a sports doctor’s research.
In other words the knuckle toughening is a myth.