I also had this problem on a freshly installed Debian Testing, I had to
run the following commands as a workaround (I got them from the ArchWiki):
xfconf-query -c xfce4-keyboard-shortcuts -p
/commands/custom/XF86AudioRaiseVolume -n -t string -s "amixer set Master
5%+ unmute"
xfconf-query -c xfce4-keyboard-shortcuts -p
/commands/custom/XF86AudioLowerVolume -n -t string -s "amixer set Master
5%- unmute"
xfconf-query -c xfce4-keyboard-shortcuts -p
/commands/custom/XF86AudioMute -n -t string -s "amixer set Master toggle"
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