Photoelectrochemical water splitting is a promising route for the renewable production of hydrogen fuel. This work presents the results of a technical and economic feasibility analysis conducted for four hypothetical, centralized, large-scale hydrogen production plants based on this technology. The four reactor types considered were a single bed particle suspension system, a dual bed particle suspension system, a fixed panel array, and a tracking concentrator array. The current performance of semiconductor absorbers and electrocatalysts were considered to compute reasonable solar-tohydrogen conversion efficiencies for each of the four systems. The U.S. Department of Energy H2A model was employed to calculate the levelized cost of hydrogen output at the plant gate at 300 psi for a 10 tonne per day production scale. All capital expenditures and operating costs for the reactors and auxiliaries (compressors, control systems, etc.) were considered. The final cost varied from $1.60-$10.40 per kg H 2 with the particle bed systems having lower costs than the panel-based systems. However, safety concerns due to the cogeneration of O 2 and H 2 in a single bed system and long molecular transport lengths in the dual bed system lead to greater uncertainty in their operation. A sensitivity analysis revealed that improvement in the solar-to-hydrogen efficiency of the panel-based systems could substantially drive down their costs. A key finding is that the production costs are consistent with the Department of Energy's targeted threshold cost of $2.00-$4.00 per kg H 2 for dispensed hydrogen, demonstrating that photoelectrochemical water splitting could be a viable route for hydrogen production in the future if material performance targets can be met. Broader contextAs global energy consumption continues to rise, it is imperative that we develop renewable alternatives to the fossil fuel energy sources that currently power our civilization, curb CO 2 emissions, and secure a permanent energy supply for the future. Although the solutions to these global challenges are likely to consist of many different energy storage and conversion technologies, sustainably produced chemical fuels will likely play an important role due to their high energy density. Hydrogen gas is an especially promising energy carrier, but current hydrogen production processes such as steam methane reforming are unsustainable. Photoelectrochemical (PEC) water splitting is an alternative process that enables sustainable hydrogen production from water using the energy from sunlight. PEC water splitting has been demonstrated on the laboratory scale, but it has never been implemented on a large scale relevant to the global energy demand, so the prospects for scaling up this process have remained controversial. The present paper addresses the technical and economic feasibility of plants producing hydrogen via PEC water splitting. We establish practical operating efficiencies for PEC reactors, detail four potential reactor and centralized plant designs, and discuss the...

Photoelectrochemical (PEC) water splitting for hydrogen production is a promising technology that uses sunlight and water to produce renewable hydrogen with oxygen as a by-product. In the expanding field of PEC hydrogen production, the use of standardized

A cobalt-phosphate based oxygen evolution catalyst (Co-Pi OEC) was electrochemically deposited onto the surface of a porous bismuth vanadate electrode doped with 2 atom% Mo (BiV 0.98 Mo 0.02 O 4 ). The porous BiV 0.98 Mo 0.02 O 4 electrode was prepared using a surfactant assisted metal-organic decomposition technique at 500 C. The comparison of the photocurrent-voltage characteristics of the BiV 0.98 Mo 0.02 O 4 electrodes with and without the presence of Co-Pi catalyst demonstrated that the Co-Pi catalyst enhanced the anodic photocurrent of the BiV 0.98 Mo 0.02 O 4 electrode with its effect more pronounced at lower potentials. A stable photocurrrent density of 1.0 mA cm À2 at 1.0 V vs. Ag/AgCl was achieved under standard AM 1.5 illumination using 0.5M Na 2 SO 4 aqueous solution in phosphate buffer at pH7. Relative to the BiV 0.98 Mo 0.02 O 4 electrode, a sustained enhancement, nearly doubled photocurrent density was observed at 1.0 V vs. Ag/AgCl for Co-Pi/BiV 0.98 Mo 0.02 O 4 composite photoelectrode. Significant performance gains are obtained on BiV 0.98 Mo 0.02 O 4 electrodes upon modification with Co-Pi water oxidation catalyst.

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