In my limited experience I would say missions because the high value rats are in low sec space, but you can do level 4 missions in high spec space which have loads of high value NPCs to kill.
Wormholes (bearholes!) are by far the most profitable Rewards vs Time
Then you get the following
True sec Ratting (true lowsec ratting in npc systems) OR 0.0 Lvl 4 missions (running missions for Sansha/Guristas/Angel/Serpentis)
Ratting in 0,0 sov space (non true lowsec) OR LVL4 Missions in Empire
Bear in mind - once you have solid lvl 4 access in empire you should have good faction standing. At this point it's worth your time reading up on research agents and doing some lvl1 and 2 missions for reasearch corps for your faction. This should give you access to lvl 3 / 4 research agents and they can give you a decent passive income.
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