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It is not enough, if you just create an item.
It needs to be enabled for purchasing and available in the master org (inventory organization that is configured as item validating org in the Purchasing --> Financial options menu).
If you are new to apps, the best thing is to use copy item menu to create a new item or use the purchasing template to create new items.
Else, you can use, one time items (i.e only provide item descriptions in the req\po along with category) and create req\po.