I highly recommend visiting the niagara parks power station museum on the Canadian side - they have a very interesting exhibition of the old power plant. You can even go down to the old tunnel and walk through it to see how the water was diverted back into the river, fascinating stuff.
The Welland canal is also very interesting. There's something really cool about seeing a large ship moving _on_ a bridge while driving under that same bridge with a car. Also, the city of Welland has some nice bike trails iirc.
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