xmlns="...."
is default namespace (unprefixed namespace declaration). Note that descendant elements inherit ancestor default namespace implicitly, unless otherwise specified. That means, in this particular XML, all elements are in the default namespace.
To select element in namespace using XPath, you need to register prefix that point to the corresponding namespace first, then use the registered prefix properly in your XPath :
XmlDocument doc = new XmlDocument();
doc.Load("c:/key.xml");
var nsManager = new XmlNamespaceManager(doc.NameTable);
nsManager.Add("d", "http://www.microsoft.com/networking/WLAN/profile/v1");
XmlNode node = doc.DocumentElement.SelectSingleNode("//d:WLANProfile/d:name", nsManager);
XMLOutput.Text = node.InnerText;