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Earth-Abundant Materials for Solar Hydrogen Generation


McKone, James Robert (2013) Earth-Abundant Materials for Solar Hydrogen Generation. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/NDDJ-P611.


A critical challenge for the 21st century is shifting from the predominant use of fossil fuels to renewables for energy. Among many options, sunlight is the only single renewable resource with sufficient abundance to replace most or all of our current fossil energy use. However, existing photovoltaic and solar thermal technologies cannot be scaled infinitely due to the temporal and geographic intermittency of sunlight. Therefore efficient and inexpensive methods for storage of solar energy in a dense medium are needed in order to greatly increase utilization of the sun as a primary resource. For this purpose we have proposed an artificial photosynthetic system consisting of semiconductors, electrocatalysts, and polymer membranes to carry out photoelectrochemical water splitting as a method for solar fuel generation.

This dissertation describes efforts over the last five years to develop critical semiconductor and catalyst components for efficient and scalable photoelectrochemical hydrogen evolution, one of the half reactions for water splitting. We identified and developed Ni–Mo alloy and Ni2P nanoparticles as promising earth-abundant electrocatalysts for hydrogen evolution. We thoroughly characterized Ni–Mo alloys alongside Ni and Pt catalysts deposited onto planar and structured Si light absorbers for solar hydrogen generation. We sought to address several key challenges that emerged in the use of non-noble catalysts for solar fuels generation, resulting in the synthesis and characterization of Ni–Mo nanopowder for use in a new photocathode device architecture. To address the mismatch in stability between non-noble metal alloys and Si absorbers, we also synthesized and characterized p-type WSe2 as a candidate light absorber alternative to Si that is stable under acidic and alkaline conditions.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:solar; artificial photosynthesis; electrolysis; catalyst; hydrogen; electrochemistry; photoelectrochemistry; semiconductor; tungsten; selenide; nickel; phosphide; molybdenum; Ni-Mo
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:Milton and Frances Clauser Doctoral Prize, 2013. Everhart Distinguished Graduate Student Lecturer Award, 2013. Demetriades-Tsafka-Kokkalis Prize in Environmentally Benign Renewable Energy Sources or Related Fields, 2013.
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Gray, Harry B. (co-advisor)
  • Lewis, Nathan Saul (co-advisor)
Thesis Committee:
  • Okumura, Mitchio (chair)
  • Miller, Thomas F.
  • Peters, Jonas C.
  • Gray, Harry B.
  • Lewis, Nathan Saul
Defense Date:23 May 2013
Non-Caltech Author Email:mckone (AT)
Funding AgencyGrant Number
National Science FoundationCHE-0802907
Department of EnergyDE-AC05-06OR23100
Department of EnergyDE-FG02-03ER15483
Record Number:CaltechTHESIS:06052013-140402659
Persistent URL:
McKone, James Robert0000-0001-6445-7884
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7844
Deposited By: James McKone
Deposited On:06 Jun 2013 22:39
Last Modified:04 Oct 2019 00:01

Thesis Files

PDF (Final version of thesis) - Final Version
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