This is the bit I looked at, as I said a compromise, but if gas then likely modulating, i.e. variable output, likely between 6 and 28 kW and this is done in the main so the return water is cool enough for the boiler to extract the latent heat from flue gases.
So with a modulating wall thermostat in the main room, this is possible, but Hive does not modulate. Whole idea of Hive is control is by the TRV heads but there is a upper limit of 22°C for the wall thermostat, above this limit it will not accept any demands for heat. So the on/off wall thermostat is placed in a room with no alternative heating, on the lower floor, with no outside door and normally kept cool, often no such room so hall is often used, its job is to stop boiler cycling in the summer, Hive is a little more flexible as it can accept a call for heat from linked TRV heads unless at 22°C or over, but the wall thermostat is still there to switch off whole heating system to stop cycling or if geofencing is enabled when your not at home.
With oil where the boiler does not modulate maybe on/off thermostat is fitted in main room, but with gas only if using a modulating thermostat.
When you turn off a boiler any heat in boiler is lost out of the flue, and when turned on with on/off thermostat or programmer it starts at maximum output, so boiler gets hot quick, if turned on by the boiler as return water cools then turns on at minimum output, same if turned on by a modulating thermostat.
So idea is to avoid on/off switching as much as possible, clearly turns off when you leave house or go to bed, but each time is switches off the boilers internal system is reset. So the TRV is king, since the TRV turns up/down rather than on/off it does two things, one it allows the boiler to run more economical, and two it reduces the hysteresis to a minimum.
The problem with non linked TRV control is it can't turn the boiler on, so we select key rooms to be linked.
The problem is so often central heating is not set up. The hard bit is setting of the lock shield valve, closed too far and room will not get warm enough, everyone understands that, but open too far and the boiler gets hot water returned premature, and the TRV can't close fast enough to stop a hysteresis starting, normally start setting is around 15°C drop feed to return on radiator.
To my mind biggest problem is TRV marked *123456 we know we want say 20°C but we have no idea if that equals 2 or 4, and in real terms there is no exact number that = 20°C likely around 2.5 but depends on room size and radiator size. If you take a standard TRV and try blowing through it, at 20°C you will realise it starts to close at around 4 and fully closed at 2 it is an analogue device.
With electronic TRV heads even the cheap ones at £15 each
View attachment 251959 it shows °C. This means you know setting on TRV so now it is simple, if temperature over shoots you close the lock shield valve a small amount, and repeat until it does not over shoot. You only have one variable. Once lock shield set you could return to old type TRV and these work great, unless you want a programmed change, but you need one set correct so you can set the other.