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"Substitute" and "switch" are synonyms as they both refer to replacing something with another. However, they are not homophones which are words that sound the same but have different meanings. An antonym of "substitute" could be "original" or "primary" as they denote opposing ideas.
The answer is that there is no homophone for can, but can is a homonym.
The homophone for "hymn" is "him."
Your is a homophone of you're. In some dialects, yore is another homophone.
the homophone for stationery is stationary