Rationalism is referring to rational behavior, and it can be based upon many kinds of evidence sources like testimony, history, empirical evidence, etc.. and so on. Critical entails a behavior of carefully analyzing something to the point where it is required. From there we can understand that critical rationalism means that the person is employing a behavior in which they are employing rationality to their thinking using different kinds of evidences as a base for their analysis.
On the other hand, empiricism entails that we are demanding about empirical evidence. Skepticism means that the person is employing a behavior of radically questioning something. So if we join both terms, it will mean that the person is asking simultaneous questions about something while demanding only empirical evidence.
So, from the above mentioned understanding we can conclude that critical rationalism is a concept and empirical skepticism is a type of critical rationalism but the latter employ a bit more strong behavior then the former.
So, I am not an expert on the field, neither do I know what these terms actually mean. But from names, I have derived this meaning which is quite sensible in my view