How to use string.substr() function?

If I am correct, the second parameter of substr() should be the length of the substring. How about

b = a.substr(i,2);

?

As shown here, the second argument to substr is the length, not the ending position:

string substr ( size_t pos = 0, size_t n = npos ) const;

Generate substring

Returns a string object with its contents initialized to a substring of the current object. This substring is the character sequence that starts at character position pos and has a length of n characters.

Your line b = a.substr(i,i+1); will generate, for values of i:

substr(0,1) = 1
substr(1,2) = 23
substr(2,3) = 345
substr(3,4) = 45  (since your string stops there).

What you need is b = a.substr(i,2);

You should also be aware that your output will look funny for a number like 12045. You'll get 12 20 4 45 due to the fact that you're using atoi() on the string section and outputting that integer. You might want to try just outputing the string itself which will be two characters long:

b = a.substr(i,2);
cout << b << " ";

In fact, the entire thing could be more simply written as:

#include <iostream>
#include <string>
using namespace std;
int main(void) {
    string a;
    cin >> a;
    for (int i = 0; i < a.size() - 1; i++)
        cout << a.substr(i,2) << " ";
    cout << endl;
    return 0;
}