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For  ex-situ  co-doping methods, sintering at high temperatures enables rapid diffusion of Sn 4+  and Be 2+  dopants into hematite (α–Fe 2 O 3 ) lattices, without altering the nanorod morphology or damaging their crystallinity. Sn/Be co-doping results in a remarkable enhancement in photocurrent (1.7 mA/cm 2 ) compared to pristine α–Fe 2 O 3  (0.7 mA/cm 2 ), and Sn 4+  mono-doped α-Fe 2 O 3  photoanodes (1.0 mA/cm 2 ). From first-principles calculations, we found that Sn 4+  doping induced a shallow donor level below the conduction band minimum, which does not contribute to increase electrical conductivity and photocurrent because of its localized nature. Additionally, Sn 4+ -doping induce local micro-strain and a decreased Fe-O bond ordering. When Be 2+  was co-doped with Sn 4+ -doped α–Fe 2 O 3  photoanodes, the conduction band recovered its original state, without localized impurities peaks, also a reduction in micro-strain and increased Fe-O bond ordering is observed. Also the sequence in which the  ex-situ  co-doping is carried out is very crucial, as Be/Sn co-doping sequence induces many under-coordinated O atoms resulting in a higher micro-strain and lower charge separation efficiency resulting undesired electron recombination. Here, we perform a detailed systematic characterization using XRD, FESEM, XPS and comprehensive electrochemical and photoelectrochemical studies, along with sophisticated synchrotron diffraction studies and extended X-ray absorption fine structure.

Sn/Be Sequentially co-doped Hematite Photoanodes for Enhanced Photoelectrochemical Water Oxidation: Effect of Be2+ as co-dopant