It appears that the control circuit of the boiler is extra low voltage, maybe 24V and must not be connected tot he mains supply. You'll save 10% on your Hive Radiator Valve(s) today and you can cancel Hive Heating Plus at any time.

On the twin channel one that he posted up 1 and 2 are hot water and heating off connections, 3 and 4 are the hot water and heating on connections, there isn't any volt free contacts.

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Yes, you can connect your thermostat with other Hive devices using the Hive app – for example you can boost the heating when a Hive Motion Sensor detects movement. Hive Thermostats can be used to support wet underfloor heating systems (which provide heat using pipes) but they do not currently support electric underfloor heating systems.

The receiver talks to the Thermostat which then talks to the Hive hub which is ethernet connected to the router.