Journal
ACS CATALYSIS
Volume 7, Issue 11, Pages 8006-8022Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.7b02662
Keywords
photocatalysis; water splitting; electrocatalysis; hydrogen evolution; oxygen evolution; band alignment; chemical potential; Fermi level
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Funding
- King Abdullah University of Science and Technology (KAUST)
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A widely used term, photocatalysis, generally addresses photocatalytic (energetically downhill) and photosynthetic (energetically uphill) reactions and refers to the use of photonic energy as a driving force for chemical transformations, i.e., electron reorganization to form/break chemical bonds. Although there are many such important reactions, this contribution focuses on the fundamental aspects of photocatalytic water splitting into hydrogen and oxygen by using light from the solar spectrum, which is one of the most investigated photosynthetic reactions. Photocatalytic water splitting using solar energy is considered to be artificial photosynthesis that produces a solar fuel because the reaction mimics nature's photosynthesis not only in its redox reaction type but also in its thermodynamics (water splitting: 1.23 eV vs glucose formation: 1.24 eV). To achieve efficient photocatalytic water splitting, all of the parameters, though involved at different time scales and spatial resolutions, should be optimized because the overall efficiency is obtained as the multiplication of all these fundamental efficiencies. The purpose of this Review is to provide the guidelines of a concept, photocatalysis by design, which is the opposite of black box screening; this concept refers to making quantitative descriptions of the associated physical and chemical properties to determine which events/parameters have the most impact on improving the overall photocatalytic performance, in contrast to arbitrarily ranking different photocatalyst materials. First, the properties that can be quantitatively measured or calculated are identified. Second, the quantities of these identified properties are determined by performing adequate measurements and/or calculations. Third, the obtained values of these properties are integrated into equations so that the kinetic/energetic bottlenecks of specific properties/processes can be determined, and the properties can then be altered to further improve the process. Accumulation of knowledge ranging in fields from solid-state physics to electrochemistry and the use of a multidisciplinary approach to conduct measurements and modeling in a quantitative manner are required to fully understand and improve the efficiency of photocatalysis.
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