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I'm also thinking it's a sleeping gas,Luffy has a resistance to poison,we don't know how far does the gas gas fruit can go,he might be able to create any kind of gas,and there are many types,sleeping gas is one of them which seems to be the case here.
Also it seems to me that most of the crew has a knowledge of Haki,not all of them might control it,but they know about it,in my opinion Luffy just assumed that Zoro and Sanji know Haki because they beat Caribou together,he doesn't know for sure about the rest of the crew.
So even if some them might not be able to use Haki yet,I'm sure their main goal these past 2 years was to develop a counter to the Logia guys,because they suffer the most from Logias.
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