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      Modeling integrated photovoltaic-electrochemical devices using steady-state equivalent circuits

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      Proceedings of the National Academy of Sciences
      Proceedings of the National Academy of Sciences

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          Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts.

          We describe the development of solar water-splitting cells comprising earth-abundant elements that operate in near-neutral pH conditions, both with and without connecting wires. The cells consist of a triple junction, amorphous silicon photovoltaic interfaced to hydrogen- and oxygen-evolving catalysts made from an alloy of earth-abundant metals and a cobalt|borate catalyst, respectively. The devices described here carry out the solar-driven water-splitting reaction at efficiencies of 4.7% for a wired configuration and 2.5% for a wireless configuration when illuminated with 1 sun (100 milliwatts per square centimeter) of air mass 1.5 simulated sunlight. Fuel-forming catalysts interfaced with light-harvesting semiconductors afford a pathway to direct solar-to-fuels conversion that captures many of the basic functional elements of a leaf.
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            The artificial leaf.

            To convert the energy of sunlight into chemical energy, the leaf splits water via the photosynthetic process to produce molecular oxygen and hydrogen, which is in a form of separated protons and electrons. The primary steps of natural photosynthesis involve the absorption of sunlight and its conversion into spatially separated electron-hole pairs. The holes of this wireless current are captured by the oxygen evolving complex (OEC) of photosystem II (PSII) to oxidize water to oxygen. The electrons and protons produced as a byproduct of the OEC reaction are captured by ferrodoxin of photosystem I. With the aid of ferrodoxin-NADP(+) reductase, they are used to produce hydrogen in the form of NADPH. For a synthetic material to realize the solar energy conversion function of the leaf, the light-absorbing material must capture a solar photon to generate a wireless current that is harnessed by catalysts, which drive the four electron/hole fuel-forming water-splitting reaction under benign conditions and under 1 sun (100 mW/cm(2)) illumination. This Account describes the construction of an artificial leaf comprising earth-abundant elements by interfacing a triple junction, amorphous silicon photovoltaic with hydrogen- and oxygen-evolving catalysts made from a ternary alloy (NiMoZn) and a cobalt-phosphate cluster (Co-OEC), respectively. The latter captures the structural and functional attributes of the PSII-OEC. Similar to the PSII-OEC, the Co-OEC self-assembles upon oxidation of an earth-abundant metal ion from 2+ to 3+, may operate in natural water at room temperature, and is self-healing. The Co-OEC also activates H(2)O by a proton-coupled electron transfer mechanism in which the Co-OEC is increased by four hole equivalents akin to the S-state pumping of the Kok cycle of PSII. X-ray absorption spectroscopy studies have established that the Co-OEC is a structural relative of Mn(3)CaO(4)-Mn cubane of the PSII-OEC, where Co replaces Mn and the cubane is extended in a corner-sharing, head-to-tail dimer. The ability to perform the oxygen-evolving reaction in water at neutral or near-neutral conditions has several consequences for the construction of the artificial leaf. The NiMoZn alloy may be used in place of Pt to generate hydrogen. To stabilize silicon in water, its surface is coated with a conducting metal oxide onto which the Co-OEC may be deposited. The net result is that immersing a triple-junction Si wafer coated with NiMoZn and Co-OEC in water and holding it up to sunlight can effect direct solar energy conversion via water splitting. By constructing a simple, stand-alone device composed of earth-abundant materials, the artificial leaf provides a means for an inexpensive and highly distributed solar-to-fuels system that employs low-cost systems engineering and manufacturing. Through this type of system, solar energy can become a viable energy supply to those in the non-legacy world.
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              Mechanistic studies of the oxygen evolution reaction by a cobalt-phosphate catalyst at neutral pH.

              The mechanism of the oxygen evolution reaction (OER) by catalysts prepared by electrodepositions from Co(2+) solutions in phosphate electrolytes (Co-Pi) was studied at neutral pH by electrokinetic and (18)O isotope experiments. Low-potential electrodepositions enabled the controlled preparation of ultrathin Co-Pi catalyst films (<100 nm) that could be studied kinetically in the absence of mass transport and charge transport limitations to the OER. The Co-Pi catalysts exhibit a Tafel slope approximately equal to 2.3 × RT/F for the production of oxygen from water in neutral solutions. The electrochemical rate law exhibits an inverse first order dependence on proton activity and a zeroth order dependence on phosphate for [Pi] ≥ 0.03 M. In the absence of phosphate buffer, the Tafel slope is increased ∼3-fold and the overall activity is greatly diminished. Together, these electrokinetic studies suggest a mechanism involving a rapid, one electron, one proton equilibrium between Co(III)-OH and Co(IV)-O in which a phosphate species is the proton acceptor, followed by a chemical turnover-limiting process involving oxygen-oxygen bond coupling.
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                Author and article information

                Journal
                Proceedings of the National Academy of Sciences
                Proceedings of the National Academy of Sciences
                Proceedings of the National Academy of Sciences
                0027-8424
                1091-6490
                March 19 2013
                March 04 2013
                : 110
                : 12
                : E1076-E1082
                Article
                10.1073/pnas.1301532110
                5ebc0f04-abec-4e1c-a21e-b4fdbe2ce0db
                © 2013
                Product
                Self URI (article page): http://www.pnas.org/cgi/doi/10.1073/pnas.1301532110

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