Well, sorry to have to say it, but your brother's impression of where he could park with his resident permit is wrong. This bay is obviously not meant for long term parking, but obviously, your brother can park there outside the controlled hours of Mon-Sat 8am to 6.30pm, and also for two hours within those times. From your narrative, and looking at the PCN, clearly he parked outside the controlled hours, and then came within the controlled times at 8am, so would have been in contravention at 10am.
However, there is a 10 minute grace period when a vehicle is parked in a designated parking place, and over-runs the time allowed, so the PCN has been issued too early at 10.07. The two hours parking allowed, started at 8am, and ended at 10am, therefore a PCN could not lawfully be served before 10.10am. So it seems this CEO is in need of additional training !
You should therefore submit an informal challenge stating that the PCN was served too early as there is a 10 minute grace period allowed when the parking over-runs the allowed times.