Good question. Here are my picks:-
1960s -From Russia With Love - chilling introduction of one of the best Bond movie henchmen, Grant - not for the first time in that film you think, albeit briefly, that Bond has "had it" at the hands of SPECTRE's chief executioner. Goldfinger, because it is a bit like a mini James Bond film - gadgets, fights, explosions, Bond gets the girl (briefly), another fight and a one line witticism ("Shocking, positively shocking") and You Only Live Twice - because of the outer space scene. John Barry's "Capsule In Space" ramps up the tension, and you just know that US astronaut isn't going to survive his spacewalk.
1970s- The Man With The Golden Gun unusual because it focuses almost entirely on the villain of the piece. Also, inevitably The Spy Who Loved Me for the ski chase scene.
1980s- Had it not been for a totally misjudged use of background music I might have gone for A View To A Kill. However, I'll plump for the PTC from The Living Daylights which like the Goldfinger PTC is a mini Bond film in itself (But, unlike Goldfinger's PTC actually has something to do with the rest of the film.) Also for outrageous use of a horsebox and an Acrostar jet plane, I'll vote for Octopussy as well!
1990s- Tough, because we have three more "Bond movies in a nutshell" type PTCs here, but I'll plump for GoldenEye because of the spectacular opening shot and overlook Bond's apparent ability to defy the laws of gravity! Tomorrow Never Dies was something of a Bond movie within a Bond movie - all those top brass and M watching our hero on TV.
2000s- Casino Royale strictly speaking the PTC was the black and white intercutting of Bond's brutal pummelling of his first kill and his cold, clinical despatch of the MI6 traitor Dryden. Again, unusual for Bond and very well done. I'll mention the parkour chase as well, as in any other Bond film that scene would most likely have been straight after a traditional gunbarrel/Bond theme opener and before the theme tune.
2010s- Until something better comes along, it has to be the PTC from Skyfall. It's a good one anyway - not only full of action but it sets up the relationship with Eve Moneypenny - and the tension later between Bond and M - and leaves us wondering, however briefly, about Bond's fate at the end.