Proving Postorder Traversal's Time Complexity
In order to prove the complexity of n-vertex tree, you must first understand how to analyze the time for a binary tree. So i am explaining it for a binary tree so that you can generalize it.

In postorder traversal each node in binary tree is visited:

a) 1 time if it is a leaf node.

b) 1 time if it is a node with only one child (either left or right)

c) 2 times if the node has both left and right children. 2 times because when we have to process the right child once we have finished with processing of its left child we need to check whether the node has right child or not. If it has a right child we process right child deferring the parent node so that it could be revisited again once we are finished with processing of right child as well.

So, any node in the tree is not visited more than two times. If n is the number of nodes then the worst case complexity is $O(2n)$ (in case of complete binary tree) and best case is $O(n)$ (in case of skew tree). Ignoring the constants:

Best case time : $O(n)$

Worst case time : $O(n)$

Hence, we can say algorithm is $Θ(n)$.