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Spain, winners in 2010 and unbeaten since Euro 2016, topped a difficult Group B and now face a big obstacle in the shape of the hosts, who will be backed by a partisan crowd in Luzhniki.
In the evening match, Croatia take on Denmark in Nizhny Novgorod.
The winners from today’s matches will face each other in the quarter-finals in Sochi next weekend.
The knock-out phase started in dramatic fashion on Saturday.
The early kick-off saw a World Cup classic ensue as France defeated Argentina 4-3.
Antoine Griezmann opened the scoring from the spot after the brilliant Kylian Mbappe was upended inside the box by Marcos Rojo.
But Angel Di Maria’s stunning long-range effort saw Argentina draw level, before Gabriel Mercado’s fortunate goal put them ahead.
Benjamin Pavard scored a wonderful half-volley to equalise, and then Mbappe, superb throughout, became the first teenager to score two in a World Cup match since Pele netted twice for Brazil against Sweden in the 1958 final to put France 4-2 ahead.
Aguero’s fine header set up a tense finish, but France held on to progress to the last eight.
And Uruguay, impressive throughout the tournament, knocked Bernardo Silva’s Portugal out of the competition after a 2-1 win.
Edinson Cavani's header gave Uruguay the lead after seven minutes, but Pepe equalised 10 minutes after half-time to set up an intriguing contest.
But Cavani struck again late on with a sensational first-time finish into the bottom corner to see Oscar Tabarez’s side through to the next round.
It’s the World Cup that keeps on giving…
France 4-3 Argentina
Uruguay 2-1 Portugal
Spain v Russia – 3pm BBC One
Croatia v Denmark – 7pm ITV
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