In this report, we show that by creating a nanoporous haematite (aFe 2 O 3 ) structure using boric acid (H 3 BO 3 ) treatment, the chronic issue of the short diffusion length of carriers in a-Fe 2 O 3 for photo- Photoelectrochemical (PEC) water splitting cells which use solar energy to produce hydrogen or oxygen gas are a promising technology for solving the energy crisis and environmental problems. 1-6 Since Fujishima and Honda rst reported a PEC water splitting system using a titanium dioxide semiconductor, n-type semiconductors have been considered to be promising photoanode materials for PEC water splitting cells.7,8 Hematite (a-Fe 2 O 3 ) is a very attractive material among n-type semiconductors for PEC water splitting because of its relatively narrow band gap (2.1-2.2 eV) and superior chemical stability in electrolytes.9,10 More importantly, compared to rare semiconductor materials (As, Ga, In, Se, and so on), which are commonly used in monolithic photovoltaic-PEC cells, a-Fe 2 O 3 is very cheap and abundant, and therefore, able to achieve high solar-to-hydrogen (STH) efficiency economically. The elemental doping of a-Fe 2 O 3 uses a relatively simple procedure and has attracted much attention as a way to improve a-Fe 2 O 3 performance by increasing its electronic conductivity and carrier life time. 16,[20][21][22] However, the use of rare metal dopants such as Pt, Si, and Ti and so on increases the overall price of the PEC cell. Alternatively, it has been reported that forming oxygen vacancies in semiconductors such as TiO 2 and a-Fe 2 O 3 by treatment with reducing agents could enhance the PEC performance by increasing the donor density. In particular, Fe 2+ ions in a-Fe 2 O 3 with oxygen vacancies could dramatically increase the conductivity of the a-Fe 2 O 3 via a polaron hopping mechanism.
23Controlling the nanostructure morphology of a-Fe 2 O 3 has been another efficient way to overcome the disadvantages of aFe 2 O 3 by increasing its surface area and reducing the path length of hole transport. For example, diverse morphologies of a-Fe 2 O 3 such as mesoporous nanotubes/nanowires and threedimensional nano-structures have exhibited much improved PEC performance compared to normal lm type a-Fe 2 O 3 .
24-26Although the control of a-Fe 2 O 3 morphology has produced highly enhanced performance, the fabrication process involves complex steps and the resulting particle sizes are above 50-80 nm which are still signicantly larger than the 2-4 nm hole diffusion length. 10,27 In this work, the fabrication of boric acid (H 3 BO 3 ) treated a-Fe 2 O 3 with optimized sizes using a cheap and broadly applicable hydrothermal growth method is reported. The dissociation constant of the [FeB(OH) 4 ] 2+ complex controls the rate of formation of b-FeOOH, and accounts for the nal nanoporous morphology of a-Fe 2 O 3 nanorods with $15 nm