Enabling tandem oxidation of benzene to benzenediol over integrated neighboring V-Cu oxides in mesoporous silica

• V-Cu bimetallic oxides modified nanoporous silica was constructed. • Ultrafine CuO were neighbored by VO x with strong interplay in mesopore. • The desorption of formed phenol over the catalytic site might be restricted. • Synergetic tandem-oxidation activities for benzene towards benzenediol were enabled. The direct tandem oxidation synthesis of benzenediol from benzene could simplify or even avoid the separation and purification of reaction intermediates, which is promising but challenged because of the further required immediate consecutive activation of intermediate phenol. In this work, a synergistic benzene tandem-oxidation catalyst that V-Cu bimetallic oxides modified nanoporous silica (VCu-NS) was constructed via a facile assembly strategy which involves addictive negative anion citric acid mediating the intercalation of metal-citric acid chelate in mesopore of silica and subsequent thermal calcination inducing dual-metal active site formation. Such a tactic could make amorphous VO x species well covered on the surface of mesopore, and ultrafine copper oxide particles surrounded and neighbored by highly dispersed VO x with strong interplay in mesopore, which was comprehensively confirmed by various characterizations. Benefiting from the unique V-Cu neighboring effect, the desorption of formed phenol over the catalytic site might be restricted therefore easily further activated by the formed reactive oxidative species, 3VCu-NS shows synergetic tandem-oxidation catalytic activities for benzene towards benzenediol with a selectivity of 57%. The result allows optimal 3VCu-NS to be a promising catalyst for benzenediol synthesis from benzene.