Unravelling the role of the combined effect of metallic charge transfer channel and SiO_(x) overlayer in the Zr/Si-Fe_(2)O_(3):Au:SiO_(x) nanorod arrays to boost photoelectrochemical water splitting

Hematite(α-Fe_(2)O_(3)) based photoanodes have been extensively studied due to various intriguing features that make them viable candidates for a photoelectrochemical(PEC) water splitting photoanode.Herein,we propose a Zr-doped Fe_(2)O_(3) photoanode decorated with facilely spin-coated Au nanoparticles(NPs) and microwave-assisted attached Si co-doping in conjunction with a SiO_(x) overlayer that displayed a remarkable photocurrent density of 2.01 mA/cm^(2) at 1.23 V vs.RHE.The kinetic dynamics at the photoelectrode/-electrolyte interface was examined by employing systematic electrochemical investigations.The Au NPs played a dual role in increasing PEC water splitting.First,the Schottky interface that was formed between Au NPs and Zr-Fe_(2)O_(3) lectrode ensured the prevention of electron flow from the photoanode to the metal,increasing the number of available charges as well as suppressing surface charge recombination.Second,Au extracted photoholes from the bulk of the Zr-Fe_(2)O_(3) and transported them to the outer SiO_(x) overlayer,while the SiO_(x) overlayer efficiently collected the photoholes and promoted the hole injection into the electrolyte.Further,Si co-doping enhanced bulk conductivity by reducing bulk charge transfer resistance and improving charge carrier density.This study outlines a technique to design a metallic charge transfer path with an overlayer for solar energy conversion.

Gradient Si-and Ti-doped Fe_(2)O_(3) hierarchical homojunction photoanode for efficient solar water splitting:Effect of facile microwave-assisted growth of Si-FeOOH on Ti-FeOOH nanocorals

The construction of a homojunction is an effective approach for addressing issues such as slow charge separation and charge-transfer kinetics in photoanodes.In the present work,we designed a gradient Si-and Ti-doped Fe_(2)O_(3) homojunction photoanode to improve the photoelectrochemical(PEC)performance of a Ti-doped Fe_(2)O_(3) photoanode.Ti-FeOOH nanocorals were synthesized using a hydrothermal process,and Si-FeOOH was grown on Ti-FeOOH nanocorals using a rapid and facile microwaveassisted(MW)technique.By varying the MW irradiation time,the thickness of the Si/Ti:Fe_(2)O_(3) photoanode was adjusted and an optimized 3-Si/Ti:Fe_(2)O_(3) photoelectrode was achieved with a significantly enhanced photocurrent density(1.37 mA cm^(-2) at 1.23 V vs.RHE)and a cathodic shift of the onset potential(150 mV)compared with that of bare Ti-Fe_(2)O_(3).This enhanced PEC performance can be ascribed to homojunction formation and Si gradient doping.The Si dopant increased the donor concentration and the formation of a homojunction improved the intrinsic built-in electric field,thereby promoting charge separation and charge transfer.Furthermore,the as-formed homojunction passivated the surfacetrapping states,consequently improving the charge transfer efficiency(60%at 1.23 VRHE)at the photoanode/electrolyte interface.These findings could pave the way for the microwave-assisted fabrication of diverse efficient homojunction photoanodes for PEC water splitting applications.