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The central defender beat Argentina keeper Sergio Romero to a Neymar corner and headed home the winner, deciding a game that was set to go to penalties to determine a winner.
Coach Tite named PSG star forward Neymar Jr. as his squad's full-time captain ahead of friendly against the United States.
Belgium used a combination of daring, intelligence, resilience and a bit of luck to oust World Cup favourites Brazil 2-1 in a memorable quarterfinal.
Coach Tite is sticking with his policy of rotating the captaincy and the 33-year old Inter Milan player will become the fourth man to wear the captain's armband in Russia.
The teams have progressed through different means but each arrive with confidence after rousing wins in their last starts.
Brazil's defensive record under coach Tite has been remarkable, with only six goals conceded in 25 matches, and they have been just as miserly in Russia where they have only conceded one goal.