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Nanotextured Spikes of α-Fe2O3/NiFe2O4 Composite for Efficient Photoelectrochemical Oxidation of Water

Hussain, Shabeeb, Tavakoli, Mohammad Mahdi, Waleed, Aashir, Virk, Umar Siddique, Yang, Shihe, Waseem, Amir, Fan, Zhiyong, Nadeem, Muhammad Arif
Langmuir 2018 v.34 no.12 pp. 3555-3564
absorption, anodes, catalytic activity, electric current, electrolysis, electrons, glass, hematite, oxidation, oxides, surface area
We demonstrate for the first time the application of p-NiFe₂O₄/n-Fe₂O₃ composite thin films as anode materials for light-assisted electrolysis of water. The p-NiFe₂O₄/n-Fe₂O₃ composite thin films were deposited on planar fluorinated tin oxide (FTO)-coated glass as well as on 3D array of nanospike (NSP) substrates. The effect of substrate (planar FTO and 3D-NSP) and percentage change of each component (i.e., NiFe₂O₄ and Fe₂O₃) of composite was studied on photoelectrochemical (PEC) water oxidation reaction. This work also includes the performance comparison of p-NiFe₂O₄/n-Fe₂O₃ composite (planar and NSP) devices with pure hematite for PEC water oxidation. Overall, the nanostructured p-NiFe₂O₄/n-Fe₂O₃ device with equal molar 1:1 ratio of NiFe₂O₄ and Fe₂O₃ was found to be highly efficient for PEC water oxidation as compared with pure hematite, 1:2 and 1:3 molar ratios of composite. The photocurrent density of 1:1 composite thin film on planar substrate was equal to 1.07 mA/cm² at 1.23 VRHE, which was 1.7 times higher current density as compared with pure hematite device (0.63 mA/cm² at 1.23 VRHE). The performance of p-NiFe₂O₄/n-Fe₂O₃ composites in PEC water oxidation was further enhanced by their deposition over 3D-NSP substrate. The highest photocurrent density of 2.1 mA/cm² at 1.23 VRHE was obtained for the 1:1 molar ratio p-NiFe₂O₄/n-Fe₂O₃ composite on NSP (NF1-NSP), which was 3.3 times more photocurrent density than pure hematite. The measured applied bias photon-to-current efficiency (ABPE) value of NF1-NSP (0.206%) was found to be 1.87 times higher than that of NF1-P (0.11%) and 4.7 times higher than that of pure hematite deposited on FTO-coated glass (0.044%). The higher PEC water oxidation activity of p-NiFe₂O₄/n-Fe₂O₃ composite thin film as compared with pure hematite is attributed to the Z-path scheme and better separation of electrons and holes. The increased surface area and greater light absorption capabilities of 3D-NSP devices result in further improvement in catalytic activities.