The Hammers played out a tight 1-1 draw in the first leg at Belgian side Gent, but blitzed through their opponents at the London Stadium as they reached their second European semi-final in as many seasons.
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Despite conceding first with the Belgian side going 1-0 up in the 26th minute, the Premier League side soon clicked in to gear, bringing the momentum from their recent rise in form in the league into the tie.
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With Michail Antonio firing first and then Lucas Paqueta netting a penalty, West Ham's skipper then found himself on the scoresheet.
But this wasn't a goal typical of the defensive midfielder.
The 24-year-old England international picked up the ball in his natural position after Paqueta battled for possession, leaving Rice to race across the half way line all the way through to Gent's box.
Despite Antonio being available on his right, Rice turned Gent defender Joseph Okumu and hit the ball into the bottom corner, sending the London Stadium into raptures.
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Arsenal target Rice is likely to leave West Ham this summer with his contract expiring next June and the Hammers flirting with relegation this season, it marked a special moment for the Irons captain and the fans.
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talkSPORT's Adrian Durham couldn't help but heap praise on the Hammers skipper, writing on Twitter: "Wow. Declan Rice is world class. Just wow."
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Meanwhile, talkSPORT's commentator for the game, Alex Crook, tweeted: "Great second half from West Ham. That Rice goal one of those that got me off my feet in commentary."
Antonio went on to score again just after the hour mark, sealing the Hammers' 4-1 win on the night and 5-2 win on aggregate to send them into the semi-finals of a European competition for the second year in a row for the first time since 1966.
West Ham will face Dutch side AZ Alkmaar in the semis and should they go on to win the final, will secure their first title since 1980.
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