Manifesto on the Thermochemistry of Nanoscale Redox Reactions for Energy Conversion [electronic resource]

• Ngôn ngữ: eng
• Ký hiệu phân loại: 504.1 [Unassigned]
• Thông tin xuất bản: Washington, D.C. : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Science ; Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2019
• Mô tả vật lý: Size: p. 866-872 : , digital, PDF file.
• Bộ sưu tập: Metadata
• ID: 256210
• Chủ đề: 1. 30 direct energy conversion; 2. Bio-inspired; 3. Catalysis (heterogeneous); 4. Catalysis (homogeneous); 5. Et al; 6. Hydrogen and fuel cells; 7. Optics; 8. Phonons; 9. Photosynthesis (natural and artificial); 10. Solar (fuels); 11. Solar (photovoltaic)

Tóm tắt

Advancements in the use of nanoscale materials for energy conversions will rely on a clear understanding of reaction thermochemistry. While band edge and Fermi energies can be rigorous thermodynamic descriptors of bulk materials, we show here that their application to nanoscale systems is problematic. A change of one electron at a 1000 atom nanoparticle or a localized surface site on a catalyst/electrode causes significant nuclear reorganization of the system. Electron transfer is often coupled with solvent reorganization and/or with the transfer of ions, including ion intercalation, surface binding, and movement within the surrounding double layer. These effects can be significant (even for some bulk materials). However, Fermi and band energies, as typically used, do not include the energetics of nuclear reorganizations or cation coupling. A comprehensive approach to nanoscale charge transfer thermodynamics must explicitly consider these effects in order to have a more complete understanding and greater control of nanoscale redox reactivity.