Strings in Go are immutable, you can't change their content. To change the value of a string variable, you have to assign a new string value.
An easy way is to first convert the string to a byte or rune slice, do the change and convert back:
s := []byte(str[0])
s[2] = 'y'
str[0] = string(s)
fmt.Println(str)
This will output (try it on the Go Playground):
[teyt testing]
Note: I converted the string to byte slice, because this is what happens when you index a string: it indexes its bytes. A string stores the UTF-8 byte sequence of the text, which may not necessarily map bytes to characters one-to-one.
If you need to replace the 2nd character, use []rune instead:
s := []rune(str[0])
s[2] = 'y'
str[0] = string(s)
fmt.Println(str)
In this example it doesn't matter though, but in general it may.
Also note that strings.Replace() does not (necessarily) replace all occurrences:
func Replace(s, old, new string, n int) string
The parameter n tells how many replacement are to be performed max. So the following also works (try it on the Go Playground):
str[0] = strings.Replace(str[0], "s", "y", 1)
Yet another solution could be to slice the string up until the replacable character, and starting from the character after the replacable one, and just concatenate them (try this one on the Go Playground):
str[0] = str[0][:2] + "y" + str[0][3:]
Care must be taken here too: the slice indices are byte indices, not character (rune) indices.
See related question: Immutable string and pointer address