I am documenting the solution. First look here (a long discussion on xfwm4, xubuntu, xfce).
https://bugpad.net/ubuntu/+source/xfwm4/...90s.launch
Keyboard standard action or combos (pfkey, alt..) are directed with the file .config/xfce4/xfconf/xfce-perchannel-xml/xfce4-keyboard-shortcuts.xml
Mine is here (before editing).
/commands/custom/<Alt>F1 xfce4-popup-applicationsmenu
/commands/custom/<Alt>F2 xfce4-appfinder --collapsed
/commands/custom/<Alt>F2/startup-notify true
/commands/custom/<Alt>F3 xfce4-appfinder
/commands/custom/<Alt>F3/startup-notify true
/commands/custom/override true
/commands/custom/<Primary><Alt>Delete xfce4-session-logout
/commands/custom/<Primary><Alt>t x-terminal-emulator -t "Command Line"
/commands/custom/<Primary>Escape xfdesktop --menu
/commands/custom/<Primary><Shift>Escape xfce4-taskmanager
/commands/custom/Print xfce4-screenshooter
/commands/custom/<Super>h exo-open --launch FileManager
/commands/custom/<Super>l light-locker-command -l
/commands/custom/Super_L xfce4-popup-whiskermenu
/commands/custom/<Super>p xfce4-display-settings --minimal
/commands/custom/XF86Display xfce4-display-settings --minimal
/commands/custom/XF86Mail exo-open --launch MailReader
/commands/custom/XF86WWW exo-open --launch WebBrowser
/commands/default/<Alt>F1 xfce4-popup-applicationsmenu
/commands/default/<Alt>F2 xfce4-appfinder --collapsed
/commands/default/<Alt>F2/startup-notify true
/commands/default/<Alt>F3 xfce4-appfinder
/commands/default/<Alt>F3/startup-notify true
/commands/default/<Primary><Alt>Delete xflock4
/commands/default/<Primary><Alt>l xflock4
/commands/default/<Primary>Escape xfdesktop --menu
/commands/default/<Super>p xfce4-display-settings --minimal
/commands/default/XF86Display xfce4-display-settings --minimal
/commands/default/XF86Mail exo-open --launch MailReader
/commands/default/XF86WWW exo-open --launch WebBrowser
/providers <<UNSUPPORTED>>
/xfwm4/custom/<Alt>Delete del_workspace_key
/xfwm4/custom/<Alt>F10 maximize_window_key
/xfwm4/custom/<Alt>F11 fullscreen_key
/xfwm4/custom/<Alt>F12 above_key
/xfwm4/custom/<Alt>F4 close_window_key
/xfwm4/custom/<Alt>F6 stick_window_key
/xfwm4/custom/<Alt>F7 move_window_key
/xfwm4/custom/<Alt>F8 resize_window_key
/xfwm4/custom/<Alt>F9 hide_window_key
/xfwm4/custom/<Alt>Insert add_workspace_key
/xfwm4/custom/<Alt><Shift>Tab cycle_reverse_windows_key
/xfwm4/custom/<Alt>space popup_menu_key
/xfwm4/custom/<Alt>Tab cycle_windows_key
/xfwm4/custom/Down down_key
/xfwm4/custom/Escape cancel_key
/xfwm4/custom/Left left_key
/xfwm4/custom/override true
/xfwm4/custom/<Primary><Alt>d show_desktop_key
/xfwm4/custom/<Primary><Alt>Down down_workspace_key
/xfwm4/custom/<Primary><Alt>End move_window_next_workspace_key
/xfwm4/custom/<Primary><Alt>Home move_window_prev_workspace_key
/xfwm4/custom/<Primary><Alt>KP_1 move_window_workspace_1_key
/xfwm4/custom/<Primary><Alt>KP_2 move_window_workspace_2_key
/xfwm4/custom/<Primary><Alt>KP_3 move_window_workspace_3_key
/xfwm4/custom/<Primary><Alt>KP_4 move_window_workspace_4_key
/xfwm4/custom/<Primary><Alt>KP_5 move_window_workspace_5_key
/xfwm4/custom/<Primary><Alt>KP_6 move_window_workspace_6_key
/xfwm4/custom/<Primary><Alt>KP_7 move_window_workspace_7_key
/xfwm4/custom/<Primary><Alt>KP_8 move_window_workspace_8_key
/xfwm4/custom/<Primary><Alt>KP_9 move_window_workspace_9_key
/xfwm4/custom/<Primary><Alt>Left left_workspace_key
/xfwm4/custom/<Primary><Alt>Right right_workspace_key
/xfwm4/custom/<Primary><Alt>Up up_workspace_key
/xfwm4/custom/<Primary>F1 workspace_1_key
/xfwm4/custom/<Primary>F10 workspace_10_key
/xfwm4/custom/<Primary>F11 workspace_11_key
/xfwm4/custom/<Primary>F12 workspace_12_key
/xfwm4/custom/<Primary>F2 workspace_2_key
/xfwm4/custom/<Primary>F3 workspace_3_key
/xfwm4/custom/<Primary>F4 workspace_4_key
/xfwm4/custom/<Primary>F5 workspace_5_key
/xfwm4/custom/<Primary>F6 workspace_6_key
/xfwm4/custom/<Primary>F7 workspace_7_key
/xfwm4/custom/<Primary>F8 workspace_8_key
/xfwm4/custom/<Primary>F9 workspace_9_key
/xfwm4/custom/<Primary><Shift><Alt>Left move_window_left_key
/xfwm4/custom/<Primary><Shift><Alt>Right move_window_right_key
/xfwm4/custom/<Primary><Shift><Alt>Up move_window_up_key
/xfwm4/custom/Right right_key
/xfwm4/custom/<Shift><Alt>Page_Down lower_window_key
/xfwm4/custom/<Shift><Alt>Page_Up raise_window_key
/xfwm4/custom/<Super>Tab switch_window_key
/xfwm4/custom/Up up_key
/xfwm4/default/<Alt>Delete del_workspace_key
/xfwm4/default/<Alt>F10 maximize_window_key
/xfwm4/default/<Alt>F11 fullscreen_key
/xfwm4/default/<Alt>F12 above_key
/xfwm4/default/<Alt>F4 close_window_key
/xfwm4/default/<Alt>F6 stick_window_key
/xfwm4/default/<Alt>F7 move_window_key
/xfwm4/default/<Alt>F8 resize_window_key
/xfwm4/default/<Alt>F9 hide_window_key
/xfwm4/default/<Alt>Insert add_workspace_key
/xfwm4/default/<Alt><Shift>Tab cycle_reverse_windows_key
/xfwm4/default/<Alt>space popup_menu_key
/xfwm4/default/<Alt>Tab cycle_windows_key
/xfwm4/default/Down down_key
/xfwm4/default/Escape cancel_key
/xfwm4/default/Left left_key
/xfwm4/default/<Primary><Alt>d show_desktop_key
/xfwm4/default/<Primary><Alt>Down down_workspace_key
/xfwm4/default/<Primary><Alt>End move_window_next_workspace_key
/xfwm4/default/<Primary><Alt>Home move_window_prev_workspace_key
/xfwm4/default/<Primary><Alt>KP_1 move_window_workspace_1_key
/xfwm4/default/<Primary><Alt>KP_2 move_window_workspace_2_key
/xfwm4/default/<Primary><Alt>KP_3 move_window_workspace_3_key
/xfwm4/default/<Primary><Alt>KP_4 move_window_workspace_4_key
/xfwm4/default/<Primary><Alt>KP_5 move_window_workspace_5_key
/xfwm4/default/<Primary><Alt>KP_6 move_window_workspace_6_key
/xfwm4/default/<Primary><Alt>KP_7 move_window_workspace_7_key
/xfwm4/default/<Primary><Alt>KP_8 move_window_workspace_8_key
/xfwm4/default/<Primary><Alt>KP_9 move_window_workspace_9_key
/xfwm4/default/<Primary><Alt>Left left_workspace_key
/xfwm4/default/<Primary><Alt>Right right_workspace_key
/xfwm4/default/<Primary><Alt>Up up_workspace_key
/xfwm4/default/<Primary>F1 workspace_1_key
/xfwm4/default/<Primary>F10 workspace_10_key
/xfwm4/default/<Primary>F11 workspace_11_key
/xfwm4/default/<Primary>F12 workspace_12_key
/xfwm4/default/<Primary>F2 workspace_2_key
/xfwm4/default/<Primary>F3 workspace_3_key
/xfwm4/default/<Primary>F4 workspace_4_key
/xfwm4/default/<Primary>F5 workspace_5_key
/xfwm4/default/<Primary>F6 workspace_6_key
/xfwm4/default/<Primary>F7 workspace_7_key
/xfwm4/default/<Primary>F8 workspace_8_key
/xfwm4/default/<Primary>F9 workspace_9_key
/xfwm4/default/<Primary><Shift><Alt>Left move_window_left_key
/xfwm4/default/<Primary><Shift><Alt>Right move_window_right_key
/xfwm4/default/<Primary><Shift><Alt>Up move_window_up_key
/xfwm4/default/Right right_key
/xfwm4/default/<Shift><Alt>Page_Down lower_window_key
/xfwm4/default/<Shift><Alt>Page_Up raise_window_key
/xfwm4/default/<Super>Tab switch_window_key
/xfwm4/default/Up up_key
File is created from standard template located at /etc/xdg/xfce4/xfconf/xfce-perchannel-xml when you define a new user.
By default keys combo such as default (Control key) + pf12 or Alt key + pf12 are already assigned to xfwm4 or something else (please look at custom action also).
Not ALL Key combos are displayed by xfce4-keyboard-settings (from menu or from the shell). The only way to change custom action is by editing (xml file) your file located at .config/xfce4/xfconf/xfce-perchannel-xml/xfce4-keyboard-shortcuts.xml. You can also edit the standard template located at /etc/xdg/xfce4/xfconf/xfce-perchannel-xml (not recommanded...) as a standard before creating new users or before resetting your keyboard configuration using xfce4-keyboard-settings.
If you reset your keyboard settings using xfce4-keyboard-settings it also reset ALL custom action to the default. I have difficulty to understand the usefulness of having ctrl key + pf12 mapped to a switch to the twelve workspace...by default. It should be not assigned or at least should be documented. Same as using Alt+Insert (adding workspace) or Alt+Delete (deleting workspace)
In a word if you are experiencing difficulty with mapping for some applications look here FIRST.