There are no faces where the main hands follow a 24-Hour dial. There are a couple watch faces with secondary data that will do something similar, but not exactly like the face in your picture. Solar Dial and GMT.
Solar Dial: Has a 24 Hour circular track with Noon at the top and Midnight at the bottom. A single pointer tracks where the sun is relative to the 24 hour dial. The inner dial is still 12 hour, but can also be shown digitally with your clock settings in 24-Hour time if you like.
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GMT: Has an outer circular track with Noon at the bottom and Midnight at the top. There is a red pointer that will track the hour on the 24 hour dial. Only the current hour numeral will be visible on the 24 hour dial. The inner dial will still show a 12 hour clock. This one is designed to track a different time zone, but you can set it to your current location.
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Descriptions of all the watch faces:
Your Apple Watch comes with a variety of watch faces, most of which you can customize.
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