Regarding "comfort zone" versus "shockers", I'm not bothered about Bond against other series such as Batman. I'm mostly looking at the Bond series. I'd say the following qualify as shockers.
Doctor No - up until this we Brits didn't do films in which the "hero" killed a villain (Dent) and then unloaded a few more bullets into the corpse. Just not British, don't you know.
From Russia With Love - more of the same. Bond slaps Tania about and brutally kills Grant - and the moment when "Nash" is revealed as Grant is a real moment of danger for Bond.
OHMSS - no more Connery. A shock in itself.
The Living Daylights - in spite of the script, an actor playing James Bond as Ian Fleming's James Bond.
Licence To Kill - a shocker, but would have been even better with a different team working with Dalton. As it is, the old team working overtime to prove they could do "tough and brutal".
Casino Royale (2006) - I don't agree that it was a missed opportunity. The parkour chase and the mayhem at Miami airport were nods towards the expected, but the rest mostly confounded audience expectations, and it worked brilliantly. Be honest - your typical audience wouldn't have expected a scene in which a naked Bond has his prized possessions knocked about (Frankly I was shocked the scene was filmed at all.)
Quantum of Solace - A shocker because of the direction style, although if there's an argument that Skyfall borrowed from a certain director's way then surely it also applies here, given the number of films involving "shaky-cam". I was knocked back a bit by QoS, but it gets better and better every time I watch.
Skyfall - for the reasons I mentioned in a previous post. I could have added "M is killed off", which is a shocker, I suppose. One of my relations reckoned it was a "great film but not a great Bond film". I think it's both. But surely it's a shock when "great film" and "Bond film" are used in the same sentence. We've all been used to Bond films as being box office gold but apparently not worthy of critical acclaim. This film - and CR 2006 - managed both.
The rest - from GF to YOLT, from DAF to AVTAK, from GE to DAD? Comfort zone. Goldfinger set a great precedent. Two films followed it. Diamonds Are Forever set a different one - more camp, more humourous. Two more films followed that. One could argue that the Roger Moore era was one big comfort zone - two films following the lead of DAF, then five more suited to his Bond. The Brosnan era was, I thought, not a bad attempt to bring the 60s Bond into the 90s - but not ground-breaking.