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Messages - annulen
If you are on Linux, you can probably identify what is broken by using strace -e trace=file. Before first TLS connection Qt tries to open system CA certificates in their typical locations, and in strace log you will see which exact paths lead to which errors.
Firefox may be using bundled certificates or load them from a different path. Path from where Qt tries to load CA certificates depends on OS that you are using. Maybe file or directory permissions were screwed or some symlink stopped working