Try this to get the heading you want. It seems to work for me.
#
https://tex.stackexchange.com/questions/17445/how-can-i-change-the-references-to-reference-in-the-thebibliography-environm
# This makes the bibliography section title empty and un-numbered
#+latex: \renewcommand{\bibsection}{\subsection*{}}
* References
bibliographystyle:unsrt
bibliography:References.bib
>
> * I want this to say "References"
> I don't need this to say References again:
> bibliographystyle:unsrt
> bibliography:References.bib
> =================================
>
> References.bib
> =================================
> @article{SmartGuy17,
> author = {A. Smart and Handsome Guy},
> title = {Enjoying Emacs and Org-mode},
> journal = {Hacking Accounts of Freedom},
> volume = {2},
> number = {4},
> pages = {1858-1894},
> year = {2017},
> }
> =================================
>
> I hope that this helps :) . Good hacking!
>
> Org mode version 9.0.7
> GNU Emacs 24.4.1
> org-ref: Version 0.9.0
>
> -------------------------------------------------
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