M. Goncharov introduced and studied a Rota–Baxter operator on a cocommutative Hopf algebra. In the present paper we define relative Rota–Baxter operators on an arbitrary Hopf algebra. A particular case of this definition is Goncharov’s operator. On a Hopf algebra with a relative Rota–Baxter operator we define new associative operation and construct a new Hopf algebra and Hopf brace. Further, we construct Rota–Baxter operators of integer weights on some groups. The question on a possibility to define operator of zero weight on groups was formulated by X. Gao, L. Guo, Y. Liu, and Z.-C. Zhu. In the last section we construct a family of two generated Hopf algebras. This family includes some known Hopf algebras, in particular, 4-dimensional Sweedler algebra .

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