Reddit user u/ieshuagancory recently shared their work on a bot that will let you know when a Twitch streamer is playing a certain champion. The tool is called SPYHERO and it's completely free to use.
SPYHERO is likely something that many people probably never realized they wanted. While Twitch is full with plenty of one-tricks already, for people to watch gameplay of their favorite characters, this will be an especially useful tool for people interested in learning a new champion or tracking pros experimenting with new picks.
The bot constantly monitors the top 100 League of Legends Twitch streamers, and from that pool will let you know which of them is playing a specific champion. All you have to do is type in the name of the champion you'd like to see played, and it will fetch and link you to a stream. Typing the "live" command will let you know every champion that's currently being played on stream.
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If a requested champion isn't being played at the moment, you can simply subscribe to be notified when somebody starts playing it.
As SPYHERO was only created a few days ago, the devs stated that they will continue to approve upon the bot based on feedback from users.