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The Belgian international opened the scoring after 11 minutes after a brilliant pass from Christian Eriksen and headed his second seven minutes before the interval, moments after a straight red card for Samuel Scheimann.
Darren Maatsen pulled one back for Excelsior on the stroke of half-time but a converted penalty from Miralem Sulejmani and a goal from Nicolas Lodeiro sealed Ajax's first home win since August 26.
Groningen and NEC Nijmegen drew 3-3 on Saturday after Uruguayan David Texeira's hat-trick had given Groningen the lead three times.
