Por exemplo, $ export PATH=/dev/null
deve fazer isso.
[ctor@dom0 ~]$ dash
$ echo 'echo meh' > nonemptyexe
$ /usr/bin/chmod a+x ./nonemptyexe
$ nonemptyexe
dash: 3: nonemptyexe: not found
$ ./nonemptyexe
meh
$ echo $PATH
/usr/local/bin:/usr/bin:/bin:/usr/local/sbin:/usr/sbin:/home/ctor/.local/bin:/home/ctor/bin
$ export PATH=/dev/null
$ nonemptyexe
dash: 7: nonemptyexe: not found
$ ./nonemptyexe
meh
$ echo $PATH
/dev/null
$ export PATH=""
$ echo $PATH
$ nonemptyexe
meh
$ ./nonemptyexe
meh
$