Two things, one no reason why a programmer designed for CH and DHW can't be used to work two zones, but second is this picture.
That black coiled up cable seems to have an orange core, so looks like the wires for the motorised valve, you said you heard it ticking, was that simply expansion of the pipes, or the valve moving, as to if when combi fitted pipe work left behind, or if it does some thing don't know, when my dad had new central heating fitted they left loads of the old pipe work in place, not connected to anything.
You clearly want better control, that boiler looks like the one my dad had, the electric control was simply, on or off, no opentherm or any other cleaver controls, however it was a modulating boiler and worked well with the radiator thermostatic valves (TRV) so all I did was fit electronic heads the the TRV's and controlled the heating that way. eQ-3 are cheap enough found them at £10 each, OK I used an expensive one the MiHome Energenie, I had intended to fit Nest, but when mother died we sold the house, so never fitted.
Hive User Guide said:
The Hive app gives you full control over your Hive Radiator Valves, including:
- setting a temperature for each radiator
- setting a schedule to only heat rooms when you need to
- connecting your Hive Radiator Valves to your other Hive devices using Actions
If you also have a Hive thermostat you can enable Heat On Demand to automatically boost your heating when a radiator needs heat.
From that is seems you can install Hive TRV heads without needing a Hive wall thermostat, so like I did with mothers house you can start with the TRV heads then if you still need it install the Hive wall thermostat latter. The big thing is to fit a TRV head is really easy, no wiring involved.