The Frenchman beat Paolo Lorenzi of Italy 6-1 6-1 on the clay in Portugal.
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Nadal and Argentine partner Juan Monaco lost the doubles final to Italians Potito Starace and Paolo Lorenzi.
CNN: Knee injury continues to 'bother' Rafael Nadal
Elsewhere, fifth seed Robin Soderling of Sweden beat Italian wild card Paolo Lorenzi 6-1 7-5 to reach the third round.
CNN: Nadal cruises through at Rome Masters
Nadal will be seeking the eighth doubles title of his career when he and Monaco play Italians Paolo Lorenzi and Potito Starace.
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Another Spaniard, No. 12 seed Nicolas Almagro , booked his place in round two with a 6-3 7-5 6-4 defeat of Italian Paolo Lorenzi.
CNN: STORY HIGHLIGHTS
Defending champion and second seed Djokovic starts against Italy's Paolo Lorenzi.
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