I think the original question should be about talking more substantively. The other looks like a misprint to me. The OED attests these substa- adverbs:
substantially [adv.]
† substanˈtifically [adv.] ← substanˈtific
† subˈstantiously [adv.]
substanˈtivally [adv.] ← substantival
substantively [adv.]
In general, there are many words that modern grammars classify as adjectives (rather than as determiners or various other noun modifiers) which you cannot convert into adverbs merely by suffixing them with -ly via derivational morphology.
Here are some examples of things that don’t work out when you try to do that with them:
You can look for an only son, but you can’t *onlily find him.
An alert listener listens alertly, but an awake one cannot listen *awakely.
A bigger idea can never be expressed *biggerly.
Although secret plans can be divulged secretly, small plans cannot be made *smally.
You can interview an old, white, European man, but you can interview him neither *oldly nor *whitely nor *Europeanly.
If the judge gave you a deferred sentence, you still haven’t been sentenced *deferredly.
People who like twice-baked potatoes don’t cook *twice-bakedly.
Just because you find yourself blessed with kittens galore doesn’t mean you’ve been *galorely blessed.
If you went looking for men who were awake, such men could not be *awakely found.
People who support their home teams are not *homely supporting those teams. And homely people are something else altogether.
Homing pigeons are not just pigeons flown *homingly.
If the position required a professor emeritus, it could not be filled *emeritusly.
A daily gardening column is not a column published *daylily, only one published daily — even if it happens to be about daylilies. :)
Although you can extract bodily fluids, you cannot extract them *bodilily.
The only adjectives you can convert into adverbs by affixing -ly to them are those that fit into the pattern:
in an ADJECTIVE manner
Those ones you can derive adverbs of manner out of via -ly. The rest you cannot.
(Notice how this rules out adjectives that can occur only postnominally, such as galore.)
And even some fitting that pattern are normally blocked for other reason; most people aren’t comfortable with converting -ly adjectives into -lily adverbs.