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Whisk ½ cup water, 3 tablespoons soy sauce, 2 tablespoons vinegar, 1 tablespoon each sesame oil and maple syrup, 1½ teaspoons cornstarch and the grated ginger and garlic in a medium bowl until smooth.
Arrange tofu in an even layer on a large rimmed baking sheet; sprinkle with ½ teaspoon salt. Gradually sprinkle the remaining ¼ cup cornstarch over the tofu, tossing to coat and pressing gently as needed to adhere.
Heat ¼ cup oil in a large skillet over medium-high heat. Add the tofu in a single layer; cook, turning as needed, until golden brown all over, about 10 minutes. Transfer, using a slotted spoon, to a paper-towel-lined plate; reserve the remaining oil in the pan.
Add broccoli and the remaining ¼ teaspoon salt to the pan; cook over medium-high heat, stirring often, until bright green and slightly charred, about 5 minutes.
Add the soy sauce mixture and the tofu; cook, gently stirring constantly, until the sauce is thickened and the tofu and broccoli are well coated, about 2 minutes.
Serve over 2 cups rice; garnish with scallions, sesame seeds and additional toasted sesame oil, if desired.